WO2016063686A1 - Adhesive composition - Google Patents

Adhesive composition Download PDF

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Publication number
WO2016063686A1
WO2016063686A1 PCT/JP2015/077474 JP2015077474W WO2016063686A1 WO 2016063686 A1 WO2016063686 A1 WO 2016063686A1 JP 2015077474 W JP2015077474 W JP 2015077474W WO 2016063686 A1 WO2016063686 A1 WO 2016063686A1
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WO
WIPO (PCT)
Prior art keywords
mass
parts
oleic acid
adhesive composition
melamine
Prior art date
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PCT/JP2015/077474
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French (fr)
Japanese (ja)
Inventor
橋口　恒則
友理 藤井
Original Assignee
Dic株式会社
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Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2016504823A priority Critical patent/JP5935961B1/en
Publication of WO2016063686A1 publication Critical patent/WO2016063686A1/en

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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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers

Definitions

  • This invention relates to the adhesive composition from which the adhesive sheet excellent in oleic acid resistance is obtained.
  • Adhesives are widely used in various fields such as manufacturing scenes of various products including electronic devices and automobiles, and medical products represented by surgical tape.
  • Examples of the pressure-sensitive adhesive composition for improving the oleic acid resistance include, for example, 50 to 90% by mass of a (meth) acrylic acid alkyl ester (A1) having an alkyl group having 4 to 12 carbon atoms, a carboxyl group-containing monomer. (A2) 3 to 20% by mass, hydroxyl group-containing monomer (A3) 3 to 20% by mass, and (meth) acrylic acid alkyl ester (A4) 3 to 15% by mass having an alkyl group having 1 to 3 carbon atoms Contains acrylic copolymer (A) having a hydroxyl group and a carboxyl group, having a weight average molecular weight of 700,000 to 2,000,000 and a theoretical Tg of ⁇ 40 ° C. or less, and a crosslinking agent (B).
  • a pressure-sensitive adhesive composition is disclosed (see, for example, Patent Document 1).
  • the problem to be solved by the present invention is to provide a pressure-sensitive adhesive composition that provides a pressure-sensitive adhesive sheet that does not swell even when contacted with oleic acid for a long period of time and has a small change in adhesive force, and is excellent in oleic acid resistance. is there.
  • the present invention includes a urethane resin (A) that is a reaction product of a polycarbonate polyol (a1) and a polyisocyanate (a2), a melamine cross-linking agent (B), and an organic solvent (C).
  • A urethane resin
  • A1 polycarbonate polyol
  • a2 polyisocyanate
  • B melamine cross-linking agent
  • C organic solvent
  • the pressure-sensitive adhesive composition of the present invention has good coatability, and the resulting pressure-sensitive adhesive sheet has excellent adhesive force, hardly swells even when contacted with oleic acid for a long time, and has little change in adhesive force. Excellent oleic acid resistance.
  • the pressure-sensitive adhesive composition of the present invention comprises a double-sided tape used for bonding a casing constituting a portable electronic terminal, a tablet personal computer, etc., a label for imparting designability to the surface of the casing, a waterproof tape, a medical use It can be suitably used in various fields such as an adhesive tape.
  • the pressure-sensitive adhesive composition of the present invention comprises urethane resin (A), which is a reaction product of polycarbonate polyol (a1) and polyisocyanate (a2), melamine crosslinking agent (B), and organic solvent (C) as essential components. It contains.
  • the polycarbonate polyol (a1) is an essential component for obtaining excellent oleic acid resistance. Unlike an ether structure or an ester structure, a carbonate structure hardly swells or decomposes even when contacted with oleic acid, and can suppress a decrease in adhesive strength.
  • As said polycarbonate polyol (a1) what was obtained by making carbonate ester and / or phosgene react with the compound which has a 2 or more hydroxyl group by a well-known method can be used, for example.
  • carbonate ester for example, methyl carbonate, dimethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used. These compounds may be used alone or in combination of two or more.
  • Examples of the compound having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1, 3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10 -Decanediol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethylpropanoldiol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, Polytetra Ji glycol, polyhexamethylene adipate
  • the obtained polycarbonate polyol can be made into a liquid and the glass transition temperature of the urethane resin (A) can be lowered, so that excellent adhesive strength (particularly initial adhesive strength) can be obtained, and good adhesive strength and olein resistance can be obtained.
  • adhesive strength particularly initial adhesive strength
  • olein resistance good adhesive strength and olein resistance
  • the number average molecular weight of the polycarbonate polyol (a1) is preferably in the range of 700 to 5,000, more preferably in the range of 800 to 3,000, from the viewpoint that adhesion strength and oleic acid resistance can be maintained at a high level. Preferably there is.
  • the number average molecular weight of the said polycarbonate polyol (a1) shows the value measured on condition of the following by the gel permeation chromatography (GPC) method.
  • Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000” (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection amount: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • the polycarbonate polyol (a1) may be used in combination with other polyols or chain extenders as necessary.
  • polyether polyol for example, polyether polyol, polyester polyol, polybutadiene polyol, polycaprolactone polyol, acrylic polyol, dimer diol, polyisoprene polyol and the like can be used. These polyols may be used alone or in combination of two or more.
  • the chain extender can be used to adjust the adhesive force, and for example, one having a number average molecular weight in the range of 50 to 400 can be used.
  • ethylene glycol, diethylene recall, triethylene glycol, propylene Aliphatic polyol compounds such as glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4′- Aromatic polyol compounds such as dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone, etc .; water; ethylenediamine, 1,2-propanediamine, 1,6-hexame Range amine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,
  • chain extender it is preferable to use an aliphatic polyol compound from the viewpoint of suppressing discoloration over time, and excellent cohesion can be obtained by using a relatively short chain extender as a hard segment. From the standpoint of further improving the adhesive strength, it is more preferable to use 1,4-butanediol and / or ethylene glycol.
  • polyisocyanate (a2) examples include aromatic polyisocyanates such as xylylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4 ′.
  • aromatic polyisocyanates such as xylylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and naphthalene diisocyanate
  • hexamethylene diisocyanate lysine diisocyanate
  • cyclohexane diisocyanate isophorone diisocyanate
  • -Aliphatic or alicyclic polyisocyanates such as dicyclohexylmethane diisocyanate, diisocyanate methylcyclohexane, tetramethylxylylene diisocyanate and the like can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, aromatic polyisocyanate is preferably used, and diphenylmethane diisocyanate and / or toluene diisocyanate is more preferably used from the viewpoint that swelling / decomposition hardly occurs even when contacted with oleic acid and oleic acid resistance can be further improved. preferable.
  • the urethane resin (A) is preferably partially crosslinked with the melamine crosslinking agent (B) described later, and has a hydroxyl group for obtaining good initial adhesive strength and oleic acid resistance, and more preferably two or more. More preferably, it has 2 to 4 hydroxyl groups.
  • the polyol composition containing the said polycarbonate polyol (a1) with respect to the molar ratio of the isocyanate group which the said polyisocyanate (a2) has, and the said chain extender (a3) are, for example.
  • the method of making it react so that the total molar ratio with the hydroxyl group and amino group which it has may become excess is mentioned.
  • the polycarbonate polyol (a1) and the chain extender (a3) may be charged all at once or may be charged in two or more times while controlling the reaction.
  • a molar ratio (NCO / OH + NH) of the total of the hydroxyl group and amino group of the polyol composition containing the polycarbonate polyol (a1) and the chain extender (a3) and the isocyanate group of the polyisocyanate (a2) Is preferably in the range of 0.3 to 0.99 from the viewpoint that the reaction can be easily controlled and a good initial adhesive force can be obtained by the crosslinking property with the crosslinking agent (B) described later. A range of 0.9 is more preferred.
  • an alcohol solvent such as methanol or 1,3-butanediol may be added for the purpose of deactivating the remaining isocyanate groups.
  • the weight average molecular weight of the urethane resin (A) obtained by the above method is in the range of 5,000 to 40,000 from the viewpoint of obtaining good coating properties, initial adhesive strength and oleic acid resistance.
  • the range of 10,000 to 25,000 is more preferable.
  • the number average molecular weight of the urethane resin (A) is preferably in the range of 3,000 to 20,000 from the viewpoint of further improving the coating property, initial adhesive strength and oleic acid resistance. More preferably, it is in the range of 10,000 to 10,000.
  • the weight average molecular weight and number average molecular weight of the said urethane resin (A) show the value obtained by measuring similarly to the number average molecular weight of the said polycarbonate polyol (a1).
  • the melamine crosslinking agent (B) is an essential component for obtaining excellent oleic acid resistance.
  • a part of the melamine crosslinking agent (B) is presumed to be crosslinked with the hydroxyl group of the urethane resin (A), but most of the melamine crosslinking agent (B) undergoes a crosslinking reaction to form a melamine crosslinked structure. Is formed. Therefore, since the state in which the urethane resin (A) is confined in the melamine cross-linked structure is formed, the urethane resin (A), which is the main element that swells, is less likely to swell by oleic acid, and the adhesive force changes. A small pressure-sensitive adhesive sheet can be obtained.
  • Examples of the melamine crosslinking agent (B) include monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, tributyrol melamine, hexabutyrol melamine, methoxymethyl melamine, Ethoxymethyl melamine, propoxymethyl melamine, butoxymethyl melamine, hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexapentyloxymethyl melamine, hexahexyloxymethyl melamine, methoxybutyl melamine, ethoxybutyl Melamine, propoxybutyl melamine, butoxybutyl melamine and the like can be used.
  • melamine crosslinking agents may be used alone or in combination of two or more.
  • the melamine crosslinking agent (B) may be used in combination with other crosslinking agents as necessary.
  • other crosslinking agent a well-known polyisocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent etc. can be used, for example.
  • These crosslinking agents may be used alone or in combination of two or more.
  • the amount of the melamine crosslinking agent (B) used is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the urethane resin (A) from the viewpoint of initial adhesive strength and oleic acid resistance. A range of 0.1 to 5 parts by mass is more preferable.
  • organic solvent (C) examples include ester solvents such as ethyl acetate, methyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and aliphatic hydrocarbons such as heptane, hexane, cyclohexane, and methylcyclohexane. Solvent; aromatic hydrocarbon solvents such as toluene, o-xylene, m-xylene, and p-xylene can be used. These organic solvents may be used alone or in combination of two or more.
  • the amount of the organic solvent (C) used is preferably in the range of 20 to 80% by mass, more preferably in the range of 30 to 70% by mass in the pressure-sensitive adhesive composition, from the viewpoint of coating properties and drying properties. .
  • the pressure-sensitive adhesive composition of the present invention contains the components (A) to (C) as essential components, but may further contain other additives as necessary.
  • additives examples include rust preventives, thixotropic agents, dispersants, sensitizers, urethanization catalysts, polymerization inhibitors, leveling agents, tackifiers, foam stabilizers, and the like. These additives may be used alone or in combination of two or more.
  • the method of manufacturing the adhesive sheet which has is mentioned.
  • the substrate examples include polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, polyolefin, polyacrylate, polyvinyl chloride, polyethylene, polypropylene ethylene vinyl alcohol, polyurethane, polyamide, and polyimide. Sheet or film; glass or the like can be used.
  • the surface of these base materials may be subjected to mold release treatment, antistatic treatment, corona treatment and the like.
  • the thickness of the substrate is determined according to the application for which the pressure-sensitive adhesive sheet is used, and is, for example, in the range of 10 to 100 ⁇ m.
  • Examples of the method of applying the pressure-sensitive adhesive composition to the substrate include a method using an applicator, roll coater, gravure coater, reverse coater, spray coater, air knife coater, die coater, and the like.
  • the thickness of the coated adhesive composition after drying is determined according to the use for which the adhesive sheet is used, and is, for example, in the range of 5 to 100 ⁇ m.
  • Examples of the method of drying the pressure-sensitive adhesive composition after coating the pressure-sensitive adhesive composition on the substrate include a method of drying at 50 to 140 ° C. for 30 seconds to 10 minutes. Further, after the drying, further aging may be performed in the range of 30 ° C. to 50 ° C. in order to accelerate the curing reaction.
  • the gel fraction when the dried film is immersed in toluene for 24 hours is preferably in the range of 10 to 60% by mass from the viewpoint of further improving the adhesive strength, particularly the initial adhesive strength, A range of 55% by weight is more preferred.
  • the initial adhesive strength of the pressure-sensitive adhesive sheet is preferably in the range of 0.5 to 10 N / 5 mm, more preferably in the range of 1 to 8 N / 5 mm, still more preferably in the range of 2.5 to 6 N / 5 mm. is there.
  • the measuring method of the initial adhesive force of the said adhesive sheet is described in the Example mentioned later.
  • the pressure-sensitive adhesive composition of the present invention has good coatability, and the resulting pressure-sensitive adhesive sheet has a good initial adhesive force due to crosslinking, and hardly swells even when contacted with oleic acid for a long time, Moreover, it has excellent oleic acid resistance with little change in adhesive force.
  • the pressure-sensitive adhesive composition of the present invention comprises a double-sided tape used for bonding a casing constituting a portable electronic terminal, a tablet personal computer, etc., a label for imparting designability to the surface of the casing, a waterproof tape, a medical use It can be suitably used in various fields such as an adhesive tape.
  • Example 1 To 100 parts by mass of the urethane resin (A-1) obtained in Synthesis Example 1, 0.8 part by mass of tributyrol melamine (hereinafter abbreviated as “TBM”) and 0. 1 part by mass was added to obtain an adhesive composition.
  • TBM tributyrol melamine
  • Example 2 to 8 A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that the types and / or amounts of the urethane resin (A) and melamine crosslinking agent (B) used were changed as shown in Tables 1 and 2.
  • a urethane resin (A′-1) having 6,320 mPa ⁇ s and a weight average molecular weight of 18,000 was obtained.
  • Example 2 A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that the urethane resin (A′-1) obtained in Comparative Synthesis Example 1 was used instead of the urethane resin (A-1).
  • the release PET on one side of the obtained pressure-sensitive adhesive sheet was peeled off, bonded to a PET film having a thickness of 50 ⁇ m, and cut into a width of 10 mm to obtain a test piece.
  • the release PET of the test piece was peeled off and bonded to a stainless steel (SUS) plate so that the adhesion area was 10 mm ⁇ 80 mm, and 2 kg roll ⁇ 2 reciprocating pressure bonding was performed. Then, after being left for 24 hours in an atmosphere of 23 ° C. and 50% humidity, the 180 ° peel strength was measured in an atmosphere of 23 ° C. and 50% humidity in accordance with JIS K6848-1974. / 10 mm).
  • the oleic acid resistance was evaluated by the difference between the initial adhesive strength and the adhesive strength after the oleic acid resistance test.
  • the release PET film of the test piece was peeled off, placed in a petri dish containing oleic acid, and allowed to stand in an atmosphere of 23 ° C. and humidity 50%. After 3 hours, the test piece was taken out, the area was measured, and the area change was calculated from the following formula (1), which was defined as the swelling ratio (%).
  • Swelling ratio (%) ⁇ (area of test piece after oleic acid immersion) ⁇ (area of test piece before oleic acid immersion) ⁇ / (area before oleic acid immersion) (1) The case where the film was deformed and the area could not be measured was marked “-”.
  • HBM Hexabutyrolol melamine
  • the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition of the present invention has a low swelling rate with respect to oleic acid and has little change in adhesive force even after being immersed in oleic acid for 3 days.
  • Comparative Example 1 is an embodiment in which an isocyanate crosslinking agent was used instead of the melamine crosslinking agent (B), but a large decrease in adhesive strength was observed when immersed in oleic acid for 3 days.
  • Comparative Example 2 is an embodiment in which polyether polyol was used instead of polycarbonate polyol (a1), but the adhesive strength was remarkably reduced after 2 days of oleic acid soaking and decomposition after 3 days of soaking. .
  • Comparative Examples 3 to 5 are all embodiments using an acrylic resin-based pressure-sensitive adhesive composition, but all were swollen and decomposed after being immersed in oleic acid for 2 days.

Abstract

The present invention addresses the problem of providing an adhesive composition with which it is possible to obtain an adhesive sheet having excellent oleic acid resistance whereby swelling does not tend to occur and there is little change in adhesive strength even after being in contact with oleic acid for a long period of time. The present invention provides an adhesive composition that is characterized by containing a urethane resin (A), which is a reaction product of a polycarbonate polyol (a1) and a polyisocyanate (a2), a melamine crosslinking agent (B), and an organic solvent (C). This adhesive composition has extremely good coating properties, and the obtained adhesive sheet has good initial adhesive strength due to crosslinking properties, and has excellent oleic acid resistance whereby swelling does not tend to occur and there is little change in adhesive strength even after being in contact with oleic acid for a long period of time.

Description

粘着剤組成物Adhesive composition
　本発明は、耐オレイン酸性に優れる粘着シートが得られる粘着剤組成物に関する。 This invention relates to the adhesive composition from which the adhesive sheet excellent in oleic acid resistance is obtained.
　粘着剤は、電子機器や自動車をはじめとする様々な製品の製造場面や、サージカルテープに代表される医療製品など様々な分野で広く利用されている。 Adhesives are widely used in various fields such as manufacturing scenes of various products including electronic devices and automobiles, and medical products represented by surgical tape.
　その中でも、近年では人が手で触れる携帯端末等の表面シールや、内部の筐体貼り合せ用防水テープの耐久性を向上するために、耐オレイン酸性に優れる材料の開発が求められている。 Among these, in recent years, in order to improve the durability of surface seals such as portable terminals that can be touched by human hands and the waterproof tape for bonding housings inside, development of materials having excellent oleic acid resistance has been demanded.
　耐オレイン酸性の向上を目的とした粘着剤組成物としては、例えば、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が開示されている（例えば、特許文献１を参照。）。 Examples of the pressure-sensitive adhesive composition for improving the oleic acid resistance include, for example, 50 to 90% by mass of a (meth) acrylic acid alkyl ester (A1) having an alkyl group having 4 to 12 carbon atoms, a carboxyl group-containing monomer. (A2) 3 to 20% by mass, hydroxyl group-containing monomer (A3) 3 to 20% by mass, and (meth) acrylic acid alkyl ester (A4) 3 to 15% by mass having an alkyl group having 1 to 3 carbon atoms Contains acrylic copolymer (A) having a hydroxyl group and a carboxyl group, having a weight average molecular weight of 700,000 to 2,000,000 and a theoretical Tg of −40 ° C. or less, and a crosslinking agent (B). A pressure-sensitive adhesive composition is disclosed (see, for example, Patent Document 1).
　しかしながら、アクリロイル基のようなエステル結合を有するアクリル系粘着剤組成物を使用した場合には、オレイン酸に長時間接触すると、膨潤や分解が起こり、接着力が低下する問題があった。 However, when an acrylic pressure-sensitive adhesive composition having an ester bond such as an acryloyl group is used, there is a problem that swelling and decomposition occur when the oleic acid is contacted for a long time, resulting in a decrease in adhesive strength.
国際公開第２０１４／００２２０３号International Publication No. 2014/002203
　本発明が解決しようとする課題は、オレイン酸に長時間接触しても膨潤しにくく、かつ接着力の変化が少ない、耐オレイン酸性に優れる粘着シートが得られる粘着剤組成物を提供することである。 The problem to be solved by the present invention is to provide a pressure-sensitive adhesive composition that provides a pressure-sensitive adhesive sheet that does not swell even when contacted with oleic acid for a long period of time and has a small change in adhesive force, and is excellent in oleic acid resistance. is there.
　本発明は、ポリカーボネートポリオール（ａ１）及びポリイソシアネート（ａ２）の反応物であるウレタン樹脂（Ａ）と、メラミン架橋剤（Ｂ）と、有機溶剤（Ｃ）とを含有することを特徴とする粘着剤組成物を提供するものである。 The present invention includes a urethane resin (A) that is a reaction product of a polycarbonate polyol (a1) and a polyisocyanate (a2), a melamine cross-linking agent (B), and an organic solvent (C). An agent composition is provided.
　本発明の粘着剤組成物は塗工性が良好であり、得られる粘着シートは、優れた接着力を有し、オレイン酸に長時間接触しても膨潤しにくく、かつ接着力の変化が少ない耐オレイン酸性に優れるものである。 The pressure-sensitive adhesive composition of the present invention has good coatability, and the resulting pressure-sensitive adhesive sheet has excellent adhesive force, hardly swells even when contacted with oleic acid for a long time, and has little change in adhesive force. Excellent oleic acid resistance.
　従って、本発明の粘着剤組成物は、携帯電子端末やタブレットパソコン等を構成する筐体の貼り合せに用いられる両面テープ、前記筐体の表面に意匠性を付与するラベル、防水テープ、医療用粘着テープ等の様々な分野で好適に使用することができる。 Therefore, the pressure-sensitive adhesive composition of the present invention comprises a double-sided tape used for bonding a casing constituting a portable electronic terminal, a tablet personal computer, etc., a label for imparting designability to the surface of the casing, a waterproof tape, a medical use It can be suitably used in various fields such as an adhesive tape.
　本発明の粘着剤組成物は、ポリカーボネートポリオール（ａ１）及びポリイソシアネート（ａ２）の反応物であるウレタン樹脂（Ａ）と、メラミン架橋剤（Ｂ）と、有機溶剤（Ｃ）とを必須成分として含有するものである。 The pressure-sensitive adhesive composition of the present invention comprises urethane resin (A), which is a reaction product of polycarbonate polyol (a1) and polyisocyanate (a2), melamine crosslinking agent (B), and organic solvent (C) as essential components. It contains.
　前記ポリカーボネートポリオール（ａ１）は優れた耐オレイン酸性を得る上で必須の成分である。エーテル構造やエステル構造とは異なり、カーボネート構造はオレイン酸と接触しても膨潤・分解が起こりにくく、接着力の低下を抑制することができる。前記ポリカーボネートポリオール（ａ１）としては、例えば、炭酸エステル及び／又はホスゲンと、２個以上の水酸基を有する化合物とを公知の方法で反応させて得られたものを用いることができる。 The polycarbonate polyol (a1) is an essential component for obtaining excellent oleic acid resistance. Unlike an ether structure or an ester structure, a carbonate structure hardly swells or decomposes even when contacted with oleic acid, and can suppress a decrease in adhesive strength. As said polycarbonate polyol (a1), what was obtained by making carbonate ester and / or phosgene react with the compound which has a 2 or more hydroxyl group by a well-known method can be used, for example.
　前記炭酸エステルとしては、例えば、メチルカーボネート、ジメチルカーボネート、ジエチルカーボネート、シクロカーボネート、ジフェニルカーボネート等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 As the carbonate ester, for example, methyl carbonate, dimethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used. These compounds may be used alone or in combination of two or more.
　前記２個以上の水酸基を有する化合物としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、ジプロピレングリコール、１，４－ブタンジオール、１，３－ブタンジオール、１，５－ペンタンジオール、１，５－ヘキサンジオール、１，６－ヘキサンジオール、１，７－ヘプタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、３－メチル－１，５－ペンタンジオール、２－ブチル－２－エチルプロパノールジオール、ネオペンチルグリコール、１，４－シクロヘキサンジオール、１，４－シクロヘキサンジメタノール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ポリヘキサメチレンアジペート、ポリヘキサメチレンサクシネート、ポリカプロラクトン等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。これらの中でも、得られるポリカーボネートポリオールを液状とさせ、ウレタン樹脂（Ａ）のガラス転移温度を下げることができため優れた接着力（特に、初期接着力）が得られ、良好な接着力と耐オレイン酸性を両立できる点から、１，５－ペンタンジオール及び１，６－ヘキサンジオールを原料として用いることが好ましい。 Examples of the compound having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1, 3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10 -Decanediol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethylpropanoldiol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, Polytetra Ji glycol, polyhexamethylene adipate, polyhexamethylene succinate, can be used polycaprolactone. These compounds may be used alone or in combination of two or more. Among these, the obtained polycarbonate polyol can be made into a liquid and the glass transition temperature of the urethane resin (A) can be lowered, so that excellent adhesive strength (particularly initial adhesive strength) can be obtained, and good adhesive strength and olein resistance can be obtained. In view of compatibility with acidity, it is preferable to use 1,5-pentanediol and 1,6-hexanediol as raw materials.
　前記 ポリカーボネートポリオール（ａ１）の数平均分子量としては、接着力と耐オレイン酸性とを高いレベルで維持できる点から、７００～５，０００の範囲であることが好ましく、８００～３，０００の範囲であることが好ましい。なお、前記ポリカーボネートポリオール（ａ１）の数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により、以下の条件にて測定した値を示す。 The number average molecular weight of the polycarbonate polyol (a1) is preferably in the range of 700 to 5,000, more preferably in the range of 800 to 3,000, from the viewpoint that adhesion strength and oleic acid resistance can be maintained at a high level. Preferably there is. In addition, the number average molecular weight of the said polycarbonate polyol (a1) shows the value measured on condition of the following by the gel permeation chromatography (GPC) method.
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
　「ＴＳＫｇｅｌ　Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成した。 Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
（標準ポリスチレン）
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－１０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－２５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－８０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１２８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２８８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－５５０」 (Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation
　前記ポリカーボネートポリオール（ａ１）には、必要に応じて、その他のポリオールや鎖伸長剤を併用してもよい。 The polycarbonate polyol (a1) may be used in combination with other polyols or chain extenders as necessary.
　前記その他のポリオールとしては、例えば、ポリエーテルポリオール、ポリエステルポリオール、ポリブタジエンポリオール、ポリカプロラクトンポリオール、アクリルポリオール、ダイマージオール、ポリイソプレンポリオール等を用いることができる。これらのポリオールは単独で用いても２種以上を併用してもよい。 As the other polyol, for example, polyether polyol, polyester polyol, polybutadiene polyol, polycaprolactone polyol, acrylic polyol, dimer diol, polyisoprene polyol and the like can be used. These polyols may be used alone or in combination of two or more.
　前記鎖伸長剤は接着力の調製に用いることができ、例えば、数平均分子量が５０～４００の範囲のものを用いることができ、具体的には、エチレングリコール、ジエチレンリコール、トリエチレングリコール、プロピレングリコール、１，３－プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール、ヘキサメチレングリコール、サッカロース、メチレングリコール、グリセリン、ソルビトール等の脂肪族ポリオール化合物；ビスフェノールＡ、４，４’－ジヒドロキシジフェニル、４，４’－ジヒドロキシジフェニルエーテル、４，４’－ジヒドロキシジフェニルスルホン、水素添加ビスフェノールＡ、ハイドロキノン等の芳香族ポリオール化合物；水；エチレンジアミン、１，２－プロパンジアミン、１，６－ヘキサメチレンジアミン、ピペラジン、２－メチルピペラジン、２，５－ジメチルピペラジン、イソホロンジアミン、４，４’－ジシクロヘキシルメタンジアミン、３，３’－ジメチル－４，４’－ジシクロヘキシルメタンジアミン、１，２－シクロヘキサンジアミン、１，４－シクロヘキサンジアミン、アミノエチルエタノールアミン、ヒドラジン、ジエチレントリアミン、トリエチレンテトラミン、イソホロンジアミン等のアミン化合物を用いることができる。前記鎖伸長剤を用いる場合には、継時的な変色を抑制できる点から脂肪族ポリオール化合物を用いることが好ましく、ハードセグメントとして比較的短い鎖伸長剤を用いることで優れた凝集力が得られ、接着力を一層向上させることができることから、１，４－ブタンジオール及び／又はエチレングリコールを用いることがより好ましい。 The chain extender can be used to adjust the adhesive force, and for example, one having a number average molecular weight in the range of 50 to 400 can be used. Specifically, ethylene glycol, diethylene recall, triethylene glycol, propylene Aliphatic polyol compounds such as glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4′- Aromatic polyol compounds such as dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone, etc .; water; ethylenediamine, 1,2-propanediamine, 1,6-hexame Range amine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexane Amine compounds such as diamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, triethylenetetramine, and isophoronediamine can be used. When using the chain extender, it is preferable to use an aliphatic polyol compound from the viewpoint of suppressing discoloration over time, and excellent cohesion can be obtained by using a relatively short chain extender as a hard segment. From the standpoint of further improving the adhesive strength, it is more preferable to use 1,4-butanediol and / or ethylene glycol.
　前記ポリイソシアネート（ａ２）としては、例えば、キシリレンジイソシアネート、フェニレンジイソシアネート、ジフェニルメタンジイソシアネート、トルエンジイソシアネート、ナフタレンジイソシアネート等の芳香族ポリイソシアネート；ヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキサンジイソシアネート、イソホロンジイソシアネート、４，４’－ジシクロヘキシルメタンジイソシアネート、ジイソシアナートメチルシクロヘキサン、テトラメチルキシリレンジイソシアネート等の脂肪族又は脂環式ポリイソシアネートなどを用いることができる。これらのポリイソシアネートは単独で用いても２種以上を併用してもよい。これらの中でも、オレイン酸と接触しても膨潤・分解が起こりにくく、耐オレイン酸性を一層向上できる点から、芳香族ポリイソシアネートを用いることが好ましく、ジフェニルメタンジイソシアネート及び／又はトルエンジイソシアネートを用いることがより好ましい。 Examples of the polyisocyanate (a2) include aromatic polyisocyanates such as xylylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4 ′. -Aliphatic or alicyclic polyisocyanates such as dicyclohexylmethane diisocyanate, diisocyanate methylcyclohexane, tetramethylxylylene diisocyanate and the like can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, aromatic polyisocyanate is preferably used, and diphenylmethane diisocyanate and / or toluene diisocyanate is more preferably used from the viewpoint that swelling / decomposition hardly occurs even when contacted with oleic acid and oleic acid resistance can be further improved. preferable.
　前記ウレタン樹脂（Ａ）は後述するメラミン架橋剤（Ｂ）と一部架橋し、良好な初期接着力及び耐オレイン酸性を得る上で水酸基を有するものであることが好ましく、より好ましくは２個以上、更に好ましくは２～４個の範囲の水酸基を有するものである。 The urethane resin (A) is preferably partially crosslinked with the melamine crosslinking agent (B) described later, and has a hydroxyl group for obtaining good initial adhesive strength and oleic acid resistance, and more preferably two or more. More preferably, it has 2 to 4 hydroxyl groups.
　前記ウレタン樹脂（Ａ）の製造方法としては、例えば、前記ポリイソシアネート（ａ２）が有するイソシアネート基のモル比に対し、前記ポリカーボネートポリオール（ａ１）を含むポリオール組成物及び前記鎖伸長剤（ａ３）が有する水酸基及びアミノ基との合計モル比が過剰となるように反応させる方法が挙げられる。なお、前記反応は、後述する有機溶剤（Ｃ）中で行ってもよい。また、前記ポリカーボネートポリオール（ａ１）及び前記鎖伸長剤（ａ３）は、一括で仕込んでも、反応を制御しながら２回以上に分けて仕込んでもよい。前記ポリカーボネートポリオール（ａ１）を含むポリオール組成物及び前記鎖伸長剤（ａ３）が有する水酸基及びアミノ基との合計と、前記ポリイソシアネート（ａ２）が有するイソシアネート基とのモル比（ＮＣＯ／ＯＨ＋ＮＨ）としては、反応を制御しやすく、後述する架橋剤（Ｂ）との架橋性により良好な初期接着力が得られる点から、０．３～０．９９の範囲であることが好ましく、０．４～０．９の範囲がより好ましい。また、前記ウレタン樹脂（Ａ）の製造後には、残存するイソシアネート基を失活させる目的で、メタノール、１，３－ブタンジオール等のアルコール溶剤を添加させてもよい。 As a manufacturing method of the said urethane resin (A), the polyol composition containing the said polycarbonate polyol (a1) with respect to the molar ratio of the isocyanate group which the said polyisocyanate (a2) has, and the said chain extender (a3) are, for example. The method of making it react so that the total molar ratio with the hydroxyl group and amino group which it has may become excess is mentioned. In addition, you may perform the said reaction in the organic solvent (C) mentioned later. The polycarbonate polyol (a1) and the chain extender (a3) may be charged all at once or may be charged in two or more times while controlling the reaction. As a molar ratio (NCO / OH + NH) of the total of the hydroxyl group and amino group of the polyol composition containing the polycarbonate polyol (a1) and the chain extender (a3) and the isocyanate group of the polyisocyanate (a2) Is preferably in the range of 0.3 to 0.99 from the viewpoint that the reaction can be easily controlled and a good initial adhesive force can be obtained by the crosslinking property with the crosslinking agent (B) described later. A range of 0.9 is more preferred. In addition, after the production of the urethane resin (A), an alcohol solvent such as methanol or 1,3-butanediol may be added for the purpose of deactivating the remaining isocyanate groups.
　以上の方法により得られる前記ウレタン樹脂（Ａ）の重量平均分子量としては、良好な塗工性、初期接着力及び耐オレイン酸性が得られる点から、５，０００～４０，０００の範囲であることが好ましく、１０，０００～２５，０００の範囲がより好ましい。 The weight average molecular weight of the urethane resin (A) obtained by the above method is in the range of 5,000 to 40,000 from the viewpoint of obtaining good coating properties, initial adhesive strength and oleic acid resistance. The range of 10,000 to 25,000 is more preferable.
　また、前記ウレタン樹脂（Ａ）の数平均分子量としては、塗工性、初期接着力及び耐オレイン酸性をより一層向上できる点から、３，０００～２０，０００の範囲であることが好ましく、４，０００～１０，０００の範囲であることがより好ましい。なお、前記ウレタン樹脂（Ａ）の重量平均分子量及び数平均分子量は、前記ポリカーボネートポリオール（ａ１）の数平均分子量と同様に測定して得られた値を示す。 The number average molecular weight of the urethane resin (A) is preferably in the range of 3,000 to 20,000 from the viewpoint of further improving the coating property, initial adhesive strength and oleic acid resistance. More preferably, it is in the range of 10,000 to 10,000. In addition, the weight average molecular weight and number average molecular weight of the said urethane resin (A) show the value obtained by measuring similarly to the number average molecular weight of the said polycarbonate polyol (a1).
　前記メラミン架橋剤（Ｂ）は、優れた耐オレイン酸性を得るうえで必須の成分である。前記メラミン架橋剤（Ｂ）は、一部は前記ウレタン樹脂（Ａ）が有する水酸基との架橋することが推測されるが、大半はメラミン架橋剤（Ｂ）同士が架橋反応し、メラミン架橋構造体が形成される。よって、前記ウレタン樹脂（Ａ）が該メラミン架橋構造体に閉じ込められた状態が形成されるため、膨潤する主要素であるウレタン樹脂（Ａ）がオレイン酸により膨潤しにくく、かつ接着力の変化が少ない粘着シートが得られる。 The melamine crosslinking agent (B) is an essential component for obtaining excellent oleic acid resistance. A part of the melamine crosslinking agent (B) is presumed to be crosslinked with the hydroxyl group of the urethane resin (A), but most of the melamine crosslinking agent (B) undergoes a crosslinking reaction to form a melamine crosslinked structure. Is formed. Therefore, since the state in which the urethane resin (A) is confined in the melamine cross-linked structure is formed, the urethane resin (A), which is the main element that swells, is less likely to swell by oleic acid, and the adhesive force changes. A small pressure-sensitive adhesive sheet can be obtained.
　前記メラミン架橋剤（Ｂ）としては、例えば、モノメチロールメラミン、ジメチロールメラミン、トリメチロールメラミン、テトラメチロールメラミン、ペンタメチロールメラミン、ヘキサメチロールメラミン、トリブチロールメラミン、ヘキサブチロールメラミン、メトキシメチルメラミン、エトキシメチルメラミン、プロポキシメチルメラミン、ブトキシメチルメラミン、ヘキサメトキシメチルメラミン、ヘキサエトキシメチルメラミン、ヘキサプロポキシメチルメラミン、ヘキサブトキシメチルメラミン、ヘキサペンチルオキシメチルメラミン、ヘキサヘキシルオキシメチルメラミン、メトキシブチルメラミン、エトキシブチルメラミン、プロポキシブチルメラミン、ブトキシブチルメラミン等を用いることができる。これらのメラミン架橋剤は単独で用いても２種以上を併用してもよい。これらの中でも、良好なメラミン架橋構造体を形成しやすく、耐オレイン酸性を一層向上できる点から、トリブチロールメラミン及び／又はヘキサブチロールメラミンを用いることが好ましい。 Examples of the melamine crosslinking agent (B) include monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, tributyrol melamine, hexabutyrol melamine, methoxymethyl melamine, Ethoxymethyl melamine, propoxymethyl melamine, butoxymethyl melamine, hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexapentyloxymethyl melamine, hexahexyloxymethyl melamine, methoxybutyl melamine, ethoxybutyl Melamine, propoxybutyl melamine, butoxybutyl melamine and the like can be used. These melamine crosslinking agents may be used alone or in combination of two or more. Among these, it is preferable to use tributyrol melamine and / or hexabutyrol melamine because it is easy to form a good melamine cross-linked structure and can further improve the oleic acid resistance.
　前記メラミン架橋剤（Ｂ）には、必要に応じてその他の架橋剤を併用してもよい。前記その他の架橋剤としては、例えば、公知のポリイソシアネート架橋剤、エポキシ架橋剤、メラミン架橋剤等を用いることができる。これらの架橋剤は単独で用いても２種以上を併用してもよい。 The melamine crosslinking agent (B) may be used in combination with other crosslinking agents as necessary. As said other crosslinking agent, a well-known polyisocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent etc. can be used, for example. These crosslinking agents may be used alone or in combination of two or more.
　前記メラミン架橋剤（Ｂ）の使用量としては、初期接着力及び耐オレイン酸性の点から、前記ウレタン樹脂（Ａ）１００質量部に対して０．０１～１０質量部の範囲であることが好ましく、０．１～５質量部の範囲がより好ましい。 The amount of the melamine crosslinking agent (B) used is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the urethane resin (A) from the viewpoint of initial adhesive strength and oleic acid resistance. A range of 0.1 to 5 parts by mass is more preferable.
　前記有機溶剤（Ｃ）としては、例えば、酢酸エチル、酢酸メチル、酢酸ブチル等のエステル溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン溶剤；ヘプタン、ヘキサン、シクロヘキサン、メチルシクロヘキサン等の脂肪族炭化水素溶剤；トルエン、ｏ－キシレン、ｍ－キシレン、ｐ－キシレン等の芳香族炭化水素溶剤などを用いることができる。これらの有機溶剤は単独で用いても２種以上を併用してもよい。 Examples of the organic solvent (C) include ester solvents such as ethyl acetate, methyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and aliphatic hydrocarbons such as heptane, hexane, cyclohexane, and methylcyclohexane. Solvent; aromatic hydrocarbon solvents such as toluene, o-xylene, m-xylene, and p-xylene can be used. These organic solvents may be used alone or in combination of two or more.
　前記有機溶剤（Ｃ）の使用量としては、塗工性及び乾燥性の点から、粘着剤組成物中２０～８０質量％の範囲であることが好ましく、３０～７０質量％の範囲がより好ましい。 The amount of the organic solvent (C) used is preferably in the range of 20 to 80% by mass, more preferably in the range of 30 to 70% by mass in the pressure-sensitive adhesive composition, from the viewpoint of coating properties and drying properties. .
　本発明の粘着剤組成物は、前記（Ａ）～（Ｃ）成分を必須成分として含有するが、必要に応じてその他の添加剤を更に含有してもよい。 The pressure-sensitive adhesive composition of the present invention contains the components (A) to (C) as essential components, but may further contain other additives as necessary.
　前記その他の添加剤としては、例えば、防錆剤、チキソ付与剤、分散剤、増感剤、ウレタン化触媒、重合禁止剤、レベリング剤、粘着付与剤、整泡剤等を用いることができる。これらの添加剤は単独で用いても２種以上を併用してもよい。 Examples of the other additives include rust preventives, thixotropic agents, dispersants, sensitizers, urethanization catalysts, polymerization inhibitors, leveling agents, tackifiers, foam stabilizers, and the like. These additives may be used alone or in combination of two or more.
　本発明の粘着シートの製造方法としては、例えば、前記粘着剤組成物を基材に塗工し、乾燥させることにより、基材と前記粘着剤組成物の乾燥皮膜（＝粘着剤層）とを有する粘着シートを製造する方法が挙げられる。 As a method for producing the pressure-sensitive adhesive sheet of the present invention, for example, by applying the pressure-sensitive adhesive composition to a base material and drying it, the base material and a dry film (= pressure-sensitive adhesive layer) of the pressure-sensitive adhesive composition are obtained. The method of manufacturing the adhesive sheet which has is mentioned.
　前記基材としては、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレー等のポリエステル、ポリオレフィン、ポリアクリレート、ポリ塩化ビニル、ポリエチレン、ポリプロピレンエチレンビニルアルコール、ポリウレタン、ポリアミド、ポリイミドなどを用いて得られるシート又はフィルム；ガラスなどを使用することができる。これらの基材の表面は、離型処理、帯電防止処理、コロナ処理等が施されていてもよい。前記基材の厚さとしては、粘着シートが使用される用途に応じて決定されるが、例えば、１０～１００μｍの範囲である。 Examples of the substrate include polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, polyolefin, polyacrylate, polyvinyl chloride, polyethylene, polypropylene ethylene vinyl alcohol, polyurethane, polyamide, and polyimide. Sheet or film; glass or the like can be used. The surface of these base materials may be subjected to mold release treatment, antistatic treatment, corona treatment and the like. The thickness of the substrate is determined according to the application for which the pressure-sensitive adhesive sheet is used, and is, for example, in the range of 10 to 100 μm.
　前記基材に前記粘着剤組成物を塗工する方法としては、例えば、アプリケーター、ロールコーター、グラビアコーター、リバースコーター、スプレーコーター、エアーナイフコーター、ダイコーター等を使用する方法が挙げられる。 Examples of the method of applying the pressure-sensitive adhesive composition to the substrate include a method using an applicator, roll coater, gravure coater, reverse coater, spray coater, air knife coater, die coater, and the like.
　塗工された粘着剤組成物の乾燥後の皮膜の厚さとしては、粘着シートが使用される用途に応じて決定されるが、例えば、５～１００μｍの範囲である。 The thickness of the coated adhesive composition after drying is determined according to the use for which the adhesive sheet is used, and is, for example, in the range of 5 to 100 μm.
　前記基材上に前記粘着剤組成物を塗工した後、前記粘着剤組成物を乾燥させる方法としては、例えば、５０～１４０℃で３０秒～１０分間乾燥させる方法が挙げられる。また、前記乾燥後、硬化反応を促進する点から、３０℃～５０℃の範囲で更にエージングを行っても良い。  Examples of the method of drying the pressure-sensitive adhesive composition after coating the pressure-sensitive adhesive composition on the substrate include a method of drying at 50 to 140 ° C. for 30 seconds to 10 minutes. Further, after the drying, further aging may be performed in the range of 30 ° C. to 50 ° C. in order to accelerate the curing reaction.
　前記乾燥皮膜をトルエン中に２４時間浸漬させた際のゲル分率としては、接着力、特に初期接着力をより一層向上できる点から、１０～６０質量％の範囲であることが好ましく、２０～５５量％の範囲がより好ましい。 The gel fraction when the dried film is immersed in toluene for 24 hours is preferably in the range of 10 to 60% by mass from the viewpoint of further improving the adhesive strength, particularly the initial adhesive strength, A range of 55% by weight is more preferred.
　前記粘着シートの初期接着力としては、好ましくは０．５～１０Ｎ／５ｍｍの範囲であり、より好ましくは１～８Ｎ／５ｍｍの範囲であり、更に好ましくは２．５～６Ｎ／５ｍｍの範囲である。なお、前記粘着シートの初期接着力の測定方法は、後述する実施例にて記載する。 The initial adhesive strength of the pressure-sensitive adhesive sheet is preferably in the range of 0.5 to 10 N / 5 mm, more preferably in the range of 1 to 8 N / 5 mm, still more preferably in the range of 2.5 to 6 N / 5 mm. is there. In addition, the measuring method of the initial adhesive force of the said adhesive sheet is described in the Example mentioned later.
　以上、本発明の粘着剤組成物は塗工性が良好であり、得られる粘着シートは、架橋により良好な初期接着力を有し、かつ、オレイン酸に長時間接触しても膨潤しにくく、かつ接着力の変化が少ない耐オレイン酸性に優れるものである。 As described above, the pressure-sensitive adhesive composition of the present invention has good coatability, and the resulting pressure-sensitive adhesive sheet has a good initial adhesive force due to crosslinking, and hardly swells even when contacted with oleic acid for a long time, Moreover, it has excellent oleic acid resistance with little change in adhesive force.
　従って、本発明の粘着剤組成物は、携帯電子端末やタブレットパソコン等を構成する筐体の貼り合せに用いられる両面テープ、前記筐体の表面に意匠性を付与するラベル、防水テープ、医療用粘着テープ等の様々な分野で好適に使用することができる。 Therefore, the pressure-sensitive adhesive composition of the present invention comprises a double-sided tape used for bonding a casing constituting a portable electronic terminal, a tablet personal computer, etc., a label for imparting designability to the surface of the casing, a waterproof tape, a medical use It can be suitably used in various fields such as an adhesive tape.
　以下、実施例を用いて本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail using examples.
［合成例１］
＜ウレタン樹脂（Ａ－１）の合成＞
　攪拌機、還流冷却器、窒素導入管、温度計を備えた反応容器に、１，５－ペンタンジオール及び１，６－ヘキサンジオール系ポリカーボネートポリオール（旭化成ケミカルズ株式会社製「デュラノールＴ５６５２」、数平均分子量；２，０００、以下「１，５ＰＧ／１，６ＨＧ系ＰＣ－１」と略記する。）を５５８質量部、１，４－ブタンジオール（以下、「１，４－ＢＧ」と略記する。）を１７質量部、ジフェニルメタンジイソシアネート（以下、「ＭＤＩ」と略記する。）を８７質量部、トリフェニルホスファイトを０．７質量部、ジメチルホルムアミド（以下、「ＤＭＦ」と略記する。）を３５７質量部仕込み、８０℃まで加温して反応させた。イソシアネート基含有率が目標値になったことを確認した後、７０度まで冷却した。その後、残存するイソシアネート基を失活させる目的で１，３－ブタンジオールを０．６質量部加えて、７０℃で１時間加温し、冷却することにより、固形分；６５質量％、粘度；４５，０００ｍＰａ・ｓ、重量平均分子量；１７，１００のウレタン樹脂（Ａ－１）を得た。 [Synthesis Example 1]
<Synthesis of urethane resin (A-1)>
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 1,5-pentanediol and 1,6-hexanediol-based polycarbonate polyol (“Duranol T5652” manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight; 2,000, hereinafter abbreviated as “1,5PG / 1,6HG PC-1”), 558 parts by mass, 1,4-butanediol (hereinafter abbreviated as “1,4-BG”). 17 parts by mass, 87 parts by mass of diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”), 0.7 parts by mass of triphenyl phosphite, and 357 parts by mass of dimethylformamide (hereinafter abbreviated as “DMF”). The reaction was carried out by heating up to 80 ° C. After confirming that the isocyanate group content reached the target value, it was cooled to 70 degrees. Then, 0.63 parts by mass of 1,3-butanediol was added for the purpose of deactivating the remaining isocyanate groups, and the mixture was heated at 70 ° C. for 1 hour and cooled to obtain a solid content of 65% by mass, viscosity; A urethane resin (A-1) of 45,000 mPa · s and a weight average molecular weight of 17,100 was obtained.
［合成例２］
＜ウレタン樹脂（Ａ－２）の合成＞
　攪拌機、還流冷却器、窒素導入管、温度計を備えた反応容器に、１，５ＰＧ／１，６ＨＧ系ＰＣ－１を８５０質量部、エチレングリコール（以下、「ＥＧ」と略記する。）１７質量部、ＭＤＩを１３３質量部、トリフェニルホスファイト１質量部、ＤＭＦを１，０００質量部仕込み、８０℃まで加温して反応させた。イソシアネート基含有率が目標値になったことを確認した後、７０度まで冷却した。その後、１，３－ブタンジオールを１質量部加えて、７０℃で１時間加温し、冷却することにより、固形分；５０質量％、粘度；３，８００ｍＰａ・ｓ、重量平均分子量；１６，０００のウレタン樹脂（Ａ－２）を得た。 [Synthesis Example 2]
<Synthesis of urethane resin (A-2)>
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 850 parts by mass of 1,5PG / 1,6HG PC-1 and 17 parts by mass of ethylene glycol (hereinafter abbreviated as “EG”). Part, 133 parts by mass of MDI, 1 part by mass of triphenyl phosphite, and 1,000 parts by mass of DMF were added and heated to 80 ° C. for reaction. After confirming that the isocyanate group content reached the target value, it was cooled to 70 degrees. Thereafter, 1 part by mass of 1,3-butanediol was added, and the mixture was heated at 70 ° C. for 1 hour and cooled to obtain a solid content of 50% by mass, viscosity; 3,800 mPa · s, weight average molecular weight; 000 urethane resin (A-2) was obtained.
［合成例３］
＜ウレタン樹脂（Ａ－３）の合成＞
　攪拌機、還流冷却器、窒素導入管、温度計を備えた反応容器に、１，５ＰＧ／１，６ＨＧ系ＰＣ－１を７００質量部、１，５－ペンタンジオール及び１，６－ヘキサンジオール系ポリカーボネートポリオール（旭化成ケミカルズ株式会社製「デュラノールＴ５６５１」、数平均分子量；１，０００、以下「１，５ＰＧ／１，６ＨＧ系ＰＣ－２」と略記する。）を２３３質量部、ＭＤＩを１１７質量部、トリフェニルホスファイト１質量部、ジメチルホルムアミド９３３質量部仕込み、８０℃まで加温して反応させた。イソシアネート基含有率が目標値になったことを確認した後、７０度まで冷却した。その後、１，３－ブタンジオールを０．８質量部加えて、７０℃で１時間加温し、冷却することにより、固形分；５０質量％、粘度；８，８００ｍＰａ・ｓ、重量平均分子量；１９，０１０のウレタン樹脂（Ａ－３）を得た。 [Synthesis Example 3]
<Synthesis of urethane resin (A-3)>
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, and thermometer, 700 parts by mass of 1,5PG / 1,6HG PC-1, 1,5-pentanediol and 1,6-hexanediol polycarbonate 233 parts by mass of polyol ("Duranol T5651" manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight; 1,000, hereinafter abbreviated as "1,5PG / 1,6HG PC-2"), 117 parts by mass of MDI, 1 part by mass of triphenyl phosphite and 933 parts by mass of dimethylformamide were charged, and the reaction was carried out by heating to 80 ° C. After confirming that the isocyanate group content reached the target value, it was cooled to 70 degrees. Thereafter, 0.8 parts by mass of 1,3-butanediol was added, and the mixture was heated at 70 ° C. for 1 hour and cooled to obtain a solid content of 50% by mass, viscosity; 8,800 mPa · s, weight average molecular weight; A 19,010 urethane resin (A-3) was obtained.
［合成例４］
＜ウレタン樹脂（Ａ－４）の合成＞
　攪拌機、還流冷却器、窒素導入管、温度計を備えた反応容器に、１，５ＰＧ／１，６ＨＧ系ＰＣ－１を９３５質量部、１，４－ＢＧを３０質量部、トルエンジイソシアネート（以下、「ＴＤＩ」と略記する。）を７２質量部、トリフェニルホスファイトを０．７質量部、ＤＭＦを１０１０質量部仕込み、８０℃まで加温して反応させた。イソシアネート基含有率が目標値になったことを確認した後、７０℃まで冷却した。その後、残存するイソシアネート基を失活させる目的で１，３－ブタンジオールを０．６質量部加えて、７０℃で１時間加温し、冷却することにより、固形分；５０質量％、粘度；３，１２０ｍＰａ・ｓ、重量平均分子量；８，０００のウレタン樹脂（Ａ－４）を得た。 [Synthesis Example 4]
<Synthesis of urethane resin (A-4)>
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 935 parts by mass of 1,5PG / 1,6HG series PC-1, 30 parts by mass of 1,4-BG, toluene diisocyanate (hereinafter, 72 parts by mass, 0.7 parts by mass of triphenyl phosphite, and 1010 parts by mass of DMF were charged and heated to 80 ° C. for reaction. After confirming that the isocyanate group content had reached the target value, it was cooled to 70 ° C. Then, 0.63 parts by mass of 1,3-butanediol was added for the purpose of deactivating the remaining isocyanate groups, and the mixture was heated at 70 ° C. for 1 hour and cooled to obtain a solid content of 50% by mass and a viscosity; A urethane resin (A-4) having 3,120 mPa · s and a weight average molecular weight of 8,000 was obtained.
［合成例５］
＜ウレタン樹脂（Ａ－５）の合成＞
　攪拌機、還流冷却器、窒素導入管、温度計を備えた反応容器に、１，５ＰＧ／１，６ＨＧ系ＰＣ－１を４４０質量部、ＥＧを１０質量部、ＭＤＩを９２質量部、トリフェニルホスファイトを０．７質量部、ＤＭＦを５４２質量部仕込み、８０℃まで加温して反応させた。イソシアネート基含有率が目標値になったことを確認した後、７０℃まで冷却した。その後、残存するイソシアネート基を失活させる目的で１，３－ブタンジオールを０．６質量部加えて、７０℃で１時間加温し、冷却することにより、固形分；５０質量％、粘度；１０,３２０ｍＰａ・ｓ、重量平均分子量；２９，０００のウレタン樹脂（Ａ－５）を得た。 [Synthesis Example 5]
<Synthesis of urethane resin (A-5)>
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube and thermometer, 440 parts by mass of 1,5PG / 1,6HG PC-1, 10 parts by mass of EG, 92 parts by mass of MDI, triphenylphosphine 0.7 parts by weight of phyto and 542 parts by weight of DMF were charged and heated to 80 ° C. for reaction. After confirming that the isocyanate group content had reached the target value, it was cooled to 70 ° C. Then, 0.63 parts by mass of 1,3-butanediol was added for the purpose of deactivating the remaining isocyanate groups, and the mixture was heated at 70 ° C. for 1 hour and cooled to obtain a solid content of 50% by mass and a viscosity; A urethane resin (A-5) having a weight average molecular weight of 29,000 was obtained at 10,320 mPa · s.
［合成例６］
＜ウレタン樹脂（Ａ－６）の合成＞
　攪拌機、還流冷却器、窒素導入管、温度計を備えた反応容器に、１，５ＰＧ／１，６ＨＧ系ＰＣ－２を５００質量部、ＥＧを２０質量部、ＴＤＩを１３０質量部、トリフェニルホスファイトを０．７質量部、ＤＭＦを６５０質量部仕込み、８０℃まで加温して反応させた。イソシアネート基含有率が目標値になったことを確認した後、７０℃まで冷却した。その後、残存するイソシアネート基を失活させる目的で１，３－ブタンジオールを０．６質量部加えて、７０℃で１時間加温し、冷却することにより、固形分；５０質量％、粘度；８，５４０ｍＰａ・ｓ、重量平均分子量；２０，４００のウレタン樹脂（Ａ－６）を得た。 [Synthesis Example 6]
<Synthesis of urethane resin (A-6)>
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, and thermometer, 500 parts by mass of 1,5PG / 1,6HG PC-2, 20 parts by mass of EG, 130 parts by mass of TDI, triphenylphosphine 0.7 parts by weight of phyto and 650 parts by weight of DMF were charged and heated to 80 ° C. for reaction. After confirming that the isocyanate group content had reached the target value, it was cooled to 70 ° C. Then, 0.63 parts by mass of 1,3-butanediol was added for the purpose of deactivating the remaining isocyanate groups, and the mixture was heated at 70 ° C. for 1 hour and cooled to obtain a solid content of 50% by mass and a viscosity; A urethane resin (A-6) having 8,540 mPa · s and a weight average molecular weight of 20,400 was obtained.
［合成例７］　
＜ウレタン樹脂（Ａ－７）の合成＞
　攪拌機、還流冷却器、窒素導入管、温度計を備えた反応容器に、１，５ＰＧ／１，６ＨＧ系ＰＣ－２を５１０質量部、１，４－ＢＧを３０質量部、ＭＤＩを１６５質量部、トリフェニルホスファイトを０．７質量部、ＤＭＦを７０５質量部仕込み、８０℃まで加温して反応させた。イソシアネート基含有率が目標値になったことを確認した後、７０℃まで冷却した。その後、残存するイソシアネート基を失活させる目的で１，３－ブタンジオールを０．６質量部加えて、７０℃で１時間加温し、冷却することにより、固形分；５０質量％、粘度；３，５２０ｍＰａ・ｓ、重量平均分子量；１４，６００のウレタン樹脂（Ａ－７）を得た。 [Synthesis Example 7]
<Synthesis of urethane resin (A-7)>
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube and thermometer, 510 parts by mass of 1,5PG / 1,6HG PC-2, 30 parts by mass of 1,4-BG, and 165 parts by mass of MDI Then, 0.7 parts by mass of triphenyl phosphite and 705 parts by mass of DMF were charged, and the reaction was carried out by heating to 80 ° C. After confirming that the isocyanate group content had reached the target value, it was cooled to 70 ° C. Then, 0.63 parts by mass of 1,3-butanediol was added for the purpose of deactivating the remaining isocyanate groups, and the mixture was heated at 70 ° C. for 1 hour and cooled to obtain a solid content of 50% by mass and a viscosity; A urethane resin (A-7) having 3,520 mPa · s and a weight average molecular weight of 14,600 was obtained.
［実施例１］
　合成例１で得られたウレタン樹脂（Ａ－１）１００質量部に対して、トリブチロールメラミン（以下、「ＴＢＭ」と略記する。）を０．８質量部、ｐ－トルエンスルホン酸０．１質量部添加し、粘着剤組成物を得た。 [Example 1]
To 100 parts by mass of the urethane resin (A-1) obtained in Synthesis Example 1, 0.8 part by mass of tributyrol melamine (hereinafter abbreviated as “TBM”) and 0. 1 part by mass was added to obtain an adhesive composition.
［実施例２～８］
　用いるウレタン樹脂（Ａ）及びメラミン架橋剤（Ｂ）の種類及び／又は量を表１～２に示す通り変更した以外は実施例１と同様にして粘着剤組成物を得た。 [Examples 2 to 8]
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that the types and / or amounts of the urethane resin (A) and melamine crosslinking agent (B) used were changed as shown in Tables 1 and 2.
［比較合成例１］
　＜ウレタン樹脂（Ａ’－１）の合成＞
　攪拌機、還流冷却器、窒素導入管、温度計を備えた反応容器に、ポリテトラメチレングリコール（三菱化学株式会社製「ＰＴＭＧ－２０００」、数平均分子量；２，０００、以下「ＰＴＭＧ」と略記する。）を１，０００質量部、ＭＤＩを１０５質量部、トリフェニルホスファイトを０．７質量部、ＤＭＦを３５７質量部仕込み、８０℃まで加温して反応させた。イソシアネート基含有率が目標値になったことを確認した後、７０℃まで冷却した。その後、残存するイソシアネート基を失活させる目的で１，３－ブタンジオールを０．６質量部加えて、７０℃で１時間加温し、冷却することにより、固形分；５０質量％、粘度；６，３２０ｍＰａ・ｓ、重量平均分子量；１８，０００のウレタン樹脂（Ａ’－１）を得た。 [Comparative Synthesis Example 1]
<Synthesis of urethane resin (A'-1)>
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, and thermometer, polytetramethylene glycol ("PTMG-2000" manufactured by Mitsubishi Chemical Corporation, number average molecular weight; 2,000, hereinafter abbreviated as "PTMG") .) Was added in an amount of 1,000 parts by mass, 105 parts by mass of MDI, 0.7 parts by mass of triphenyl phosphite, and 357 parts by mass of DMF, and heated to 80 ° C. for reaction. After confirming that the isocyanate group content had reached the target value, it was cooled to 70 ° C. Then, 0.63 parts by mass of 1,3-butanediol was added for the purpose of deactivating the remaining isocyanate groups, and the mixture was heated at 70 ° C. for 1 hour and cooled to obtain a solid content of 50% by mass and a viscosity; A urethane resin (A′-1) having 6,320 mPa · s and a weight average molecular weight of 18,000 was obtained.
［比較合成例２］
＜アクリル樹脂（Ｘ－１）の合成＞
　攪拌機、還流冷却器、窒素導入管、温度計を備えた反応容器に、ブチルアクリレート８９質量部、アクリル酸１０質量部、４－ヒドロキシエチルアクリレート０．１質量部、アゾビスイソブチロニトリル０．０８質量部、酢酸エチル６３質量部、アセトン１００質量部を仕込み、撹拌下、窒素を吹き込みながら７０度まで昇温した。撹拌下７０℃にて１４時間ホールドした後、内容物を冷却し、２００メッシュ金網にて濾過し、固形分；３８質量％、粘度；５０，０００ｍＰａ・ｓ、重量平均分子量；７０万のアクリル樹脂（Ｘ－１）を得た。 [Comparative Synthesis Example 2]
<Synthesis of acrylic resin (X-1)>
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, and thermometer, 89 parts by mass of butyl acrylate, 10 parts by mass of acrylic acid, 0.1 part by mass of 4-hydroxyethyl acrylate, 0. 08 parts by mass, 63 parts by mass of ethyl acetate, and 100 parts by mass of acetone were charged, and the temperature was raised to 70 ° C. while stirring and blowing nitrogen. After holding for 14 hours at 70 ° C. with stirring, the contents are cooled and filtered through a 200 mesh wire net, solid content: 38 mass%, viscosity: 50,000 mPa · s, weight average molecular weight: 700,000 acrylic resin (X-1) was obtained.
［比較合成例３］
＜アクリル樹脂（Ｘ－２）の合成＞
　攪拌機、還流冷却器、窒素導入管、温度計を備えた反応容器に、ブチルアクリレート５９質量部、２－エチルヘキシルアクリレート３６質量部、アクリル酸質量４部、４－ヒドロキシエチルアクリレート０．１質量部、酢酸エチル９０質量部、メチルエチルケトン（以下、「ＭＥＫ」と略記する。）２５質量部を仕込み、攪拌下、窒素を吹き込みながら７２℃まで昇温した。１時間後に、予め酢酸エチルにて溶解したアゾビスイソブチロニトリル溶液０．２５質量部（固形分２０質量％）を添加した。その後、攪拌下７２℃にて３時間ホールドした後、７５℃に昇温し、テトラメチルブチルパーオキシエチルヘキサノエート０．２質量部、ｔ－へキシルパーオキシピバレート０．２質量部を添加し５時間ホールドし反応を終了した。ここに重合ロジンペンタエリスリトールエステル８質量部と不均化ロジングリセリンエステル４質量部、酢酸エチル１４質量部を投入し、固形分；５０質量％、粘度；１０，０００ｍＰａ・ｓ、重量平均分子量；４５万のアクリル樹脂（Ｘ－２）を得た。 [Comparative Synthesis Example 3]
<Synthesis of acrylic resin (X-2)>
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, and thermometer, 59 parts by mass of butyl acrylate, 36 parts by mass of 2-ethylhexyl acrylate, 4 parts by mass of acrylic acid, 0.1 part by mass of 4-hydroxyethyl acrylate, 90 parts by mass of ethyl acetate and 25 parts by mass of methyl ethyl ketone (hereinafter abbreviated as “MEK”) were charged, and the temperature was raised to 72 ° C. while blowing nitrogen under stirring. After 1 hour, 0.25 parts by mass (solid content: 20% by mass) of an azobisisobutyronitrile solution previously dissolved in ethyl acetate was added. Thereafter, the mixture was held at 72 ° C. with stirring for 3 hours, and then heated to 75 ° C., and 0.2 parts by mass of tetramethylbutyl peroxyethyl hexanoate and 0.2 parts by mass of t-hexyl peroxypivalate were added. Added and held for 5 hours to complete the reaction. 8 parts by mass of polymerized rosin pentaerythritol ester, 4 parts by mass of disproportionated rosin glycerin ester and 14 parts by mass of ethyl acetate were added thereto, solid content: 50% by mass, viscosity: 10,000 mPa · s, weight average molecular weight: 45 Ten thousand acrylic resins (X-2) were obtained.
［比較合成例４］
＜アクリル樹脂（Ｘ－３）の合成＞
　攪拌機、還流冷却管、窒素導入管、温度計を備えた反応容器に、２－エチルヘキシルアクリレート９６質量部、アクリル酸１質量部、β－カルボキシエチルアクリレート２質量部を予め混合し、その４０質量％と酢酸エチル５７質量部を攪拌機、還流冷却管、窒素導入管、温度計を備えた反応容器に仕込んだ。攪拌下、窒素を吹き込みながら７２℃まで昇温した。１時間後に、予め酢酸エチルにて溶解したアゾビスイソブチロニトリル溶液２質量部（固形分２．５質量％）を添加した。その後、攪拌下７２℃にて１時間ホールドした後、７５℃に昇温し、残りのアクリルモノマー６０質量％とテトラメチルブチルパーオキシエチルヘキサノエート０．２質量部、ｔ－へキシルパーオキシピバレート０．２質量部を添加し１０時間ホールドし反応を終了した。ここにテルペン炭化水素樹脂１５質量部と重合ロジンペンタエリスリトールエステル５質量部、ヘキサン４０質量部を投入し、固形分；５０質量％、粘度；４，０００ｍＰａ・ｓ、重量平均分子量；５０万のアクリル樹脂（Ｘ－３）を得た。 [Comparative Synthesis Example 4]
<Synthesis of acrylic resin (X-3)>
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 96 parts by mass of 2-ethylhexyl acrylate, 1 part by mass of acrylic acid, and 2 parts by mass of β-carboxyethyl acrylate were mixed in advance. And 57 parts by mass of ethyl acetate were charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer. While stirring, the temperature was raised to 72 ° C. while blowing nitrogen. After 1 hour, 2 parts by mass (solid content: 2.5% by mass) of an azobisisobutyronitrile solution previously dissolved in ethyl acetate was added. Thereafter, the mixture was held at 72 ° C. for 1 hour with stirring, and the temperature was raised to 75 ° C., and 60% by mass of the remaining acrylic monomer, 0.2 part by mass of tetramethylbutylperoxyethyl hexanoate, t-hexylperoxy 0.2 parts by mass of pivalate was added and held for 10 hours to complete the reaction. Here, 15 parts by mass of a terpene hydrocarbon resin, 5 parts by mass of polymerized rosin pentaerythritol ester, and 40 parts by mass of hexane were charged. Solid content: 50% by mass, viscosity: 4,000 mPa · s, weight average molecular weight: 500,000 acrylic Resin (X-3) was obtained.
［比較例１］
　合成例１で得られたウレタン樹脂（Ａ－１）１００質量部に対して、ヘキサメチレンジイソシアネートのイソシアヌレート化合物（以下、「ＨＤＩヌレート」と略記する。）を１．２質量部、ウレタン化触媒（ＤＩＣ株式会社製「Ｔ－８１Ｅ」）を１質量部添加し、粘着剤組成物を得た。 [Comparative Example 1]
1.2 parts by mass of an isocyanurate compound of hexamethylene diisocyanate (hereinafter abbreviated as “HDI nurate”) with respect to 100 parts by mass of the urethane resin (A-1) obtained in Synthesis Example 1. 1 part by mass (“T-81E” manufactured by DIC Corporation) was added to obtain an adhesive composition.
［比較例２］
　ウレタン樹脂（Ａ－１）の代わりに、比較合成例１で得られたウレタン樹脂（Ａ’－１）を用いた以外は実施例１と同様にして粘着剤組成物を得た。 [Comparative Example 2]
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that the urethane resin (A′-1) obtained in Comparative Synthesis Example 1 was used instead of the urethane resin (A-1).
［比較例３］
　比較合成例１で得られたアクリル樹脂（Ｘ－１）１００質量部に対して、トルエンジイソシアネートとトリメチロールプロパンとのアダクト体（以下、「ＴＤＩ－ＴＭＰ」と略記する。）を１．２質量部添加し、粘着剤組成物を得た。 [Comparative Example 3]
1.2 parts by mass of an adduct of toluene diisocyanate and trimethylolpropane (hereinafter abbreviated as “TDI-TMP”) with respect to 100 parts by mass of the acrylic resin (X-1) obtained in Comparative Synthesis Example 1. Part of the mixture was added to obtain an adhesive composition.
［比較例３］
　用いるアクリル樹脂の種類を表２に示す通り変更した以外は比較例３と同様にして粘着剤組成物を得た。 [Comparative Example 3]
A pressure-sensitive adhesive composition was obtained in the same manner as in Comparative Example 3 except that the type of acrylic resin used was changed as shown in Table 2.
［初期接着力の測定方法］
　厚さ３８μｍの離型処理が施されたポリエチレンテレフタラート（ＰＥＴ）フィルムの表面に、乾燥後の膜厚が２０μｍとなるように実施例及び比較例で得られた粘着剤組成物を塗工し、１００℃で２分間、１２０℃で２分間、１４０℃で１分間の順に乾燥した。その後、厚さ１２μｍのＰＥＴフィルムの両面に粘着剤塗工層を貼り合わせ、４０℃で３日間放置し粘着シートを得た。
　得られた粘着シートの片方の離型ＰＥＴを剥離し、厚さ５０μｍのＰＥＴフィルムに貼り合せ、１０ｍｍ幅に裁断したものを試験片とした。該試験片の離型ＰＥＴを剥離し、ステンレス（ＳＵＳ）板に対し、接着面積が１０ｍｍ×８０ｍｍとなるように貼り合せ、２ｋｇロール×２往復圧着させた。その後、２３℃、湿度５０％の雰囲気下で２４時間放置した後、２３℃、湿度５０％の雰囲気下でＪＩＳＫ６８４８－１９７４に準拠して１８０度剥離強度を測定し、これを初期接着力（Ｎ／１０ｍｍ）とした。 [Measurement method of initial adhesive strength]
The pressure-sensitive adhesive compositions obtained in Examples and Comparative Examples were applied to the surface of a polyethylene terephthalate (PET) film that had been subjected to a release treatment of 38 μm in thickness so that the film thickness after drying was 20 μm. , Dried at 100 ° C. for 2 minutes, 120 ° C. for 2 minutes, and 140 ° C. for 1 minute. Thereafter, an adhesive coating layer was bonded to both sides of a PET film having a thickness of 12 μm and allowed to stand at 40 ° C. for 3 days to obtain an adhesive sheet.
The release PET on one side of the obtained pressure-sensitive adhesive sheet was peeled off, bonded to a PET film having a thickness of 50 μm, and cut into a width of 10 mm to obtain a test piece. The release PET of the test piece was peeled off and bonded to a stainless steel (SUS) plate so that the adhesion area was 10 mm × 80 mm, and 2 kg roll × 2 reciprocating pressure bonding was performed. Then, after being left for 24 hours in an atmosphere of 23 ° C. and 50% humidity, the 180 ° peel strength was measured in an atmosphere of 23 ° C. and 50% humidity in accordance with JIS K6848-1974. / 10 mm).
［ゲル分率の測定方法］
　前記［初期接着力の測定方法］で得られた粘着シートをトルエン中に２４時間浸漬させた前後の粘着剤層の質量からゲル分率を算出した。 [Measurement method of gel fraction]
The gel fraction was calculated from the mass of the pressure-sensitive adhesive layer before and after the pressure-sensitive adhesive sheet obtained by the above [Measurement method of initial adhesive force] was immersed in toluene for 24 hours.
［耐オレイン酸性（接着力の変化）の評価方法］
　前記［初期接着力の測定方法］で得られた試験片の離型ＰＥＴを剥離し、ステンレス（ＳＵＳ）板に対し、接着面積が１０ｍｍ×８０ｍｍとなるように貼り合せ、２ｋｇロール×２往復圧着させた。その後、２３℃、湿度５０％の雰囲気下で２４時間放置した後、更にオレイン酸中に６０℃、湿度９０％の雰囲気下で２日間又は３日間放置した。その後、オレイン酸中から試験体を取り出してから１時間後に、２３℃、湿度５０％の雰囲気下でＪＩＳＫ６８４８－１９７４に準拠して１８０度剥離強度を測定し、耐オレイン酸性試験後の接着力（Ｎ／１０ｍｍ）とした。前記初期接着力と前記耐オレイン酸性試験後の接着力との差により耐オレイン酸性を評価した。 [Evaluation method of oleic acid resistance (change in adhesive strength)]
The release PET of the test piece obtained in the above [Measurement method of initial adhesive force] is peeled off and bonded to a stainless steel (SUS) plate so that the bonding area is 10 mm × 80 mm. 2 kg roll × 2 reciprocating pressure bonding I let you. Then, after being left for 24 hours in an atmosphere of 23 ° C. and 50% humidity, it was further left in oleic acid for 2 days or 3 days in an atmosphere of 60 ° C. and 90% humidity. Thereafter, one hour after taking out the test body from oleic acid, the 180 degree peel strength was measured in an atmosphere of 23 ° C. and 50% humidity in accordance with JIS K6848-1974, and the adhesive strength after the oleic acid resistance test ( N / 10 mm). The oleic acid resistance was evaluated by the difference between the initial adhesive strength and the adhesive strength after the oleic acid resistance test.
［耐オレイン酸性（膨潤率）の評価方法］
　厚さ３８μｍの離型処理が施されたポリエチレンテレフタラート（ＰＥＴ）フィルムの表面に、乾燥後の膜厚が５０μｍとなるように実施例及び比較例で得られた粘着剤組成物を塗工し、１００℃で２分間、１２０℃で２分間、１４０℃で１分間の順に乾燥した。同塗工物を２枚用意し、両者を重ね合わせて厚さ１００μｍの粘着シートとし、４０℃で３日間放置した。この粘着シートを５０ｍｍ×５０ｍｍの大きさに裁断したものを試験片とした。該試験片の離型ＰＥＴフィルムを剥離し、オレイン酸を入れたシャーレに入れ２３℃、湿度５０％の雰囲気下で放置した。３時間後に試験片を取り出し面積を測定し、下記式（１）より面積変化を算出し、これを膨潤率（％）とした。
　膨潤率（％）＝｛（オレイン酸浸漬後の試験片の面積］－（オレイン酸浸漬前の試験片の面積）｝／（オレイン酸浸漬前の面積）　（１）
　なお、皮膜が変形し面積が測定できなかったものは「－」とした。 [Evaluation method of acid resistance (swelling rate)]
The pressure-sensitive adhesive compositions obtained in Examples and Comparative Examples were applied to the surface of a polyethylene terephthalate (PET) film having a thickness of 38 μm which was subjected to a release treatment so that the film thickness after drying was 50 μm. , Dried at 100 ° C. for 2 minutes, 120 ° C. for 2 minutes, and 140 ° C. for 1 minute. Two sheets of the same coated material were prepared, and both were laminated to form an adhesive sheet having a thickness of 100 μm, which was left at 40 ° C. for 3 days. What cut | judged this adhesive sheet to the magnitude | size of 50 mm x 50 mm was used as the test piece. The release PET film of the test piece was peeled off, placed in a petri dish containing oleic acid, and allowed to stand in an atmosphere of 23 ° C. and humidity 50%. After 3 hours, the test piece was taken out, the area was measured, and the area change was calculated from the following formula (1), which was defined as the swelling ratio (%).
Swelling ratio (%) = {(area of test piece after oleic acid immersion) − (area of test piece before oleic acid immersion)} / (area before oleic acid immersion) (1)
The case where the film was deformed and the area could not be measured was marked “-”.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
表２中の略語について説明する。
「ＨＢＭ」；ヘキサブチロールメラミン Abbreviations in Table 2 will be described.
"HBM": Hexabutyrolol melamine
　本発明の粘着剤組成物により得られた粘着シートは、オレイン酸に対する膨潤率が低く、オレイン酸に３日間浸漬した後でも接着力の変化が少ないものであった。 The pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition of the present invention has a low swelling rate with respect to oleic acid and has little change in adhesive force even after being immersed in oleic acid for 3 days.
　一方、比較例１は、メラミン架橋剤（Ｂ）の代わりにイソシアネート架橋剤を用いた態様であるが、オレイン酸に３日間浸漬させた際に大きな接着力の低下がみられた。 On the other hand, Comparative Example 1 is an embodiment in which an isocyanate crosslinking agent was used instead of the melamine crosslinking agent (B), but a large decrease in adhesive strength was observed when immersed in oleic acid for 3 days.
　比較例２は、ポリカーボネートポリオール（ａ１）の代わりにポリエーテルポリオールを用いた態様であるが、オレイン酸２日浸漬後に接着力が著しく低下し、浸漬３日後には、膨潤・分解してしまった。 Comparative Example 2 is an embodiment in which polyether polyol was used instead of polycarbonate polyol (a1), but the adhesive strength was remarkably reduced after 2 days of oleic acid soaking and decomposition after 3 days of soaking. .
　比較例３～５は、いずれもアクリル樹脂系粘着剤組成物を使用した態様であるが、いずれもオレイン酸に２日間浸漬した後には、膨潤・分解してしまった。 Comparative Examples 3 to 5 are all embodiments using an acrylic resin-based pressure-sensitive adhesive composition, but all were swollen and decomposed after being immersed in oleic acid for 2 days.

Claims (5)

  1. ポリカーボネートポリオール（ａ１）及びポリイソシアネート（ａ２）の反応物であるウレタン樹脂（Ａ）と、メラミン架橋剤（Ｂ）と、有機溶剤（Ｃ）とを含有することを特徴とする粘着剤組成物。 A pressure-sensitive adhesive composition comprising a urethane resin (A) which is a reaction product of a polycarbonate polyol (a1) and a polyisocyanate (a2), a melamine crosslinking agent (B), and an organic solvent (C).
  2. 前記ウレタン樹脂（Ａ）の重量平均分子量が、５，０００～４０，０００の範囲である請求項１記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the urethane resin (A) has a weight average molecular weight in the range of 5,000 to 40,000.
  3. 前記メラミン架橋剤（Ｂ）が、トリブチロールメラミン及び／又はヘキサブチロールメラミンである請求項１記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the melamine crosslinking agent (B) is tributyrol melamine and / or hexabutyrol melamine.
  4. 前記ポリカーボネートポリオール（ａ１）が、１，６－ヘキサンジオール及び１，５－ペンタンジオールを原料とするものである請求項１記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the polycarbonate polyol (a1) is made from 1,6-hexanediol and 1,5-pentanediol.
  5. 前記ポリイソシアネート（ａ２）が、芳香族ポリイソシアネートである請求項１記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the polyisocyanate (a2) is an aromatic polyisocyanate.
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