WO2008029766A1

WO2008029766A1 - Pressure-sensitive adhesive agent and pressure-sensitive adhesive film

Info

Publication number: WO2008029766A1
Application number: PCT/JP2007/067140
Authority: WO
Inventors: Hiroyuki Kobayashi; Issei Haruta; Noboru Kojima; Ichirou Sawatari
Original assignee: Toyo Ink Mfg. Co., Ltd.
Priority date: 2006-09-08
Filing date: 2007-09-03
Publication date: 2008-03-13
Also published as: TW200813180A; TWI353375B; JP5151982B2; JPWO2008029766A1

Abstract

A pressure-sensitive adhesive agent comprising a copolymer (C) having a hydroxyl group and/or a carboxyl group and having a grass transition temperature of –60 to 0˚C and an isocyanate-type curing agent (D), wherein: (1) the copolymer (C) is produced by the radical polymerization of 15 to 35% by weight of an alkyl methacrylate (a) having no substituent, an alkyl acrylate (b) having no substituent, and a monomer (c) which has other ethylenically unsaturated double bond copolymerizable with the components (a) and (b) and comprises a monomer (c1) having a hydroxyl group and/or a carboxyl group and an ethylenically unsaturated double bond (provided that the sum total of the components (a) to (c) is 100% by weight); and (2) the copolymer (C) comprises a high-molecular-weight component (A) and a low-molecular-weight component (B).

Description

Specification

Pressure sensitive adhesive and pressure sensitive adhesive film

Technical field

[0001] The present invention relates to a pressure-sensitive adhesive and a pressure-sensitive adhesive film using the pressure-sensitive adhesive. Specifically, the present invention relates to a pressure-sensitive adhesive suitably used when an optical film is attached to an adherend such as glass. More specifically, it can be used to form a pressure-sensitive adhesive film (pressure-sensitive adhesive film) that can be peeled off without being contaminated even if it is placed under high temperature, high pressure, high temperature, and high temperature and high humidity. It relates to adhesives.

Background art

[0002] In recent years, display devices have been used in household and commercial appliances such as electronic computers, electronic watches, mobile phones, and televisions, equipment mounted on vehicles, etc., and are used under various severe conditions. There are many opportunities. Various optical films such as a polarizing film are used for display members constituting these display devices.

Various optical films such as a polarizing film and a retardation film are attached to glass or other optical films as adherends using a pressure-sensitive adhesive. After affixing to an adherend, if a defect is found in the adhering state, the polarizing film or retardation film is peeled off from the glass or the like, and a new polarizing film or retardation film is attached. This work is called “rework”. During rework, it is required that the pressure-sensitive adhesive layer does not remain on the surface of the adherend.

[0003] Incidentally, the polarizing film has a structure in which a stretched polybutyl alcohol film dyed with a pigment is sandwiched between a triacetyl cellulose-based protective film or a cycloolefin-based protective film. Polarizing films have poor dimensional stability due to the characteristics of these materials, and the change in dimensions due to film shrinkage is particularly severe under high temperature or high temperature and high humidity conditions.

[0004] When a laminate comprising an optical film / pressure-sensitive adhesive layer / adherent body is placed under high temperature or high temperature / humidity conditions, and the dimensions of the optical film change, the pressure-sensitive adhesive layer and the adherend are Bubbles are generated at the bonding interface (foaming), the optical film is lifted from the adherend, or It may come off.

Therefore, by adjusting the molecular weight or degree of cross-linking of the main polymer component of the pressure-sensitive adhesive used, the adhesive strength is increased to resist the dimensional change of the optical film and foam, float and peel even in harsh environments. Attempts have been made to prevent this from occurring.

[0005] However, if an attempt is made to resist the dimensional change of the optical film simply by increasing the adhesive force, the stress distribution due to the dimensional change of the optical film that occurs under high temperature or high temperature and high humidity conditions becomes non-uniform, Concentrate at the four corners of the optical film or at the peripheral edge. As a result, when the optical film is a polarizing film used in a liquid crystal display device, there is a problem that a so-called “light leakage phenomenon” occurs in which light leaks from the four corners and peripheral edges of the liquid crystal display device.

[0006] The following technologies have been proposed for the development of adhesives (pressure-sensitive adhesives) for attaching optical films that do not cause foaming at the interface with the adherend even under harsh conditions and do not float or peel off. I have come.

[0007] A high molecular weight (meth) acrylic copolymer which is a copolymer of an alkyl (meth) acrylate and a polymerizable monomer having reactivity with a crosslinking agent and has a weight average molecular weight of 1 million or more. And a low molecular weight (meth) acrylic copolymer having a weight average molecular weight of 30,000 or less and a polyfunctional compound having at least two functional groups capable of forming a crosslinked structure in the molecule. In addition, a polarizing plate having a layer formed from this pressure-sensitive adhesive has been proposed (Patent Document 1: Japanese Patent Laid-Open No. 10-279907).

[0008] An adhesive layer containing a (meth) acrylic resin and a dye is provided on one surface of the light-transmitting film, and the (meth) acrylic resin has a weight average molecular weight of 200,000 or more and a high molecular weight polymer. A film with a colored pressure-sensitive adhesive for an electronic display, which is composed of a low molecular weight substance having a weight average molecular weight of less than 200,000 and has a functional group, has been proposed (Patent Document 2: Japanese Patent Application Laid-Open No. 2002-372619).

[0009] As a resin component, (A) a (meth) acrylic acid ester homopolymer or copolymer having a weight average molecular weight of 500,000 to 2,000,000, and (B) a (meth) having a weight average molecular weight of 5,000 to less than 500,000 And (meth) acrylic acid ester having at least one of (A) component and (B) component having a nitrogen-containing functional group in the molecule. A pressure-sensitive adhesive composition which is a ter copolymer has been proposed! (Patent Document 3: Japanese Patent Laid-Open No. 2001-89731).

[0010] A copolymer having a weight average molecular weight of 1 million to 2 million formed by radical copolymerization of a monomer having a reactive functional group and another monomer, and a carboxylic acid in the presence of the copolymer. A copolymer (B) having a weight average molecular weight of 10,000 to 100,000, and a copolymer (A) and / or a copolymer. A pressure-sensitive adhesive composed of a polyfunctional compound having at least two reactive functional groups capable of reacting with the coalescence (B), and a pressure-sensitive adhesive layer composed of this pressure-sensitive adhesive are formed on at least one surface of the optical member. An optical member has been proposed! (Patent Document 4: Japanese Patent Laid-Open No. 2004-331697).

[0011] Furthermore, an adhesive composition comprising an alkyl (meth) acrylate copolymer, an antioxidant, and a curing agent, in which the gel fraction of the adhesive composition is adjusted, has been proposed! /, (Patent Document 5: Japanese Patent Laid-Open No. 2003-49143).

Disclosure of the invention

[0012] The pressure-sensitive adhesives described in Patent Documents 1 to 5 have been improved so that they can withstand use under severe conditions, but after being attached to an adherend such as glass, high-temperature and high-pressure When re-applying after exposure to low, high temperature, high temperature and high humidity, the adhesion between the pressure-sensitive adhesive and the glass that is the adherend has increased, so the pressure-sensitive adhesive is applied to the glass that is the adherend. a call and the force ^s in which the adhesive is left.

In the past, there was no problem if the defect was confirmed immediately after bonding, after being exposed to high temperature and high pressure, high temperature, and high temperature and high humidity. Recently, from the viewpoint of shortening the work process and recycling, the number of cases where the polarizing film is peeled off after exposure to high temperature and high pressure, high temperature and high temperature and high humidity has increased the required rework characteristics. It is summer.

[0013] Therefore, the present invention provides an adhesive interface even when an optical film having good adhesion to an optical film is attached to an adherend and exposed to a high temperature, a high pressure, a high temperature, and a high temperature and high humidity for a long time. Pressure-sensitive adhesive capable of forming a pressure-sensitive adhesive layer with excellent reworkability as well as no foaming, no floating or peeling, and no light leakage phenomenon, and using this pressure-sensitive adhesive It is an object of the present invention to provide a pressure-sensitive adhesive film. [0014] According to one aspect of the present invention, a copolymer (C) having a hydroxyl group and / or a carboxyl group and having a glass transition temperature of 60 to 0 ° C and an isocyanate curing agent (D) are provided. A pressure sensitive adhesive containing:

The copolymer (C) is

(1) Alkyl metatalylate having no substituent (a): 15 to 35% by weight, copolymerizable with V having no substituent, alkyl acrylate (b), and (a) and (b) Other monomer (c) having an ethylenically unsaturated double bond, including a monomer (cl) having a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated double bond ( c) is obtained by radical copolymerization (provided that the total of (a) to (c) is 100% by weight),

(2) including a high molecular weight component (A) and a low molecular weight component (B),

(2 1) The peak of the high molecular weight component (A1) having a weight average molecular weight of 500,000 to 2,200,000 and a weight average molecular weight of 1000 to 10; completely independent on the emission curve in gel permeation chromatography. Of low molecular weight component (B1), and the area specific force between the peak of the high molecular weight component (A1) and the peak of the low molecular weight component (B1) (A1) / (B1) = 60/40 ~ It ’s 90/10.

(2-2) The peak of the high molecular weight component (A2) having a weight average molecular weight of 500,000 to 2,200,000 and the weight average molecular weight of 1000 to 200 located on both sides of the minimum value of the emission curve in gel permeation chromatography; The area ratio between the peak of the high molecular weight component (A2) and the peak of the low molecular weight component (B2) is (A2) / (B2) = 60 / 40-90 / 10 force, or

(2-3) In gel permeation chromatography, a peak of a high molecular weight component (A3) consisting of polymer molecules having a molecular weight of 150,000 or more and a weight average molecular weight of 500,000 to 2,200,000, and a polymer having a molecular weight of less than 150,000 A low molecular weight component (B3) peak consisting of molecules having a weight average molecular weight of 1000-; and the area ratio of the high molecular weight component (A3) peak to the low molecular weight component (B3) peak is ( A3) / (B3) = 60/40 to 90/10,

A pressure sensitive adhesive is provided.

[0015] According to another aspect of the present invention, there is provided a method for producing a pressure-sensitive adhesive comprising the following (I) to (III): (I) Alkyl metatalylate having no substituent (a): 15 to 35% by weight, V having no substituent, alkyl attalate (b), and other copolymerizable with the above (a) and (b) A monomer (c) having an ethylenically unsaturated double bond and comprising a monomer (cl) having a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated double bond ( c) radically copolymerizing the polymerization conversion rate to 60 to 90% to obtain a copolymer containing a high molecular weight component having a weight average molecular weight of 500,000 to 2,200,000;

(II) Next, the monomer (c) is added as necessary, and the above-mentioned (a) to (c) are further radically copolymerized until the polymerization conversion becomes 80 to 100% (provided that (a) to (The sum of (c) is 100% by weight)),

(2-1) The peak of the high molecular weight component (A1) having a weight average molecular weight of 500,000 to 2,200,000 and a weight average molecular weight of 1000 to 1,000, completely independent on the emission curve in gel permeation chromatography; 100,000 low molecular weight component (B1) peak, and the area specific force between the high molecular weight component (A1) peak and the low molecular weight component (B1) peak (A1) / (B1) = 60/40 It is ~ 90/10

A copolymer (C) comprising a high molecular weight component (A) and a low molecular weight component (B), having a hydroxyl group and / or a carboxyl group, and having a glass transition temperature of −60 to 0 ° C. Obtaining a copolymer (C); and

(III) Mixing the copolymer (C) with the isocyanate curing agent (D). [0016] According to still another aspect of the present invention, an optical film selected from the group consisting of a polarizing film and a retardation film, and a pressure-sensitive adhesive layer provided on at least one surface of the optical film, There is provided a pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive according to one aspect of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

[0017] The pressure-sensitive adhesive according to the present invention includes a copolymer (C), which is a main component of the pressure-sensitive adhesive, and an isocyanate curing agent (D). Is formed.

The copolymer (C) has a hydroxyl group and / or a carboxyl group, and its glass transition temperature (hereinafter also referred to as “Tg”) is −60 to 0 ° C. The copolymer (C) has an alkyl metatalylate (a) having no substituent, an alkyl acrylate (b) having no substituent, and other ethylenic copolymerizable with the above (a) (b). The monomer (c) having an unsaturated double bond is a constituent component. The monomer (c) includes at least a monomer (cl) having a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated double bond.

[0018] The copolymer (C) contains a high molecular weight component (A) and a low molecular weight component (B).

There are the following three types of copolymers (C) depending on the form indicated by the discharge curve of gel permeation chromatography (hereinafter also referred to as “GPC”).

(2-1) High molecular weight component (A1) and low molecular weight component (B1) form a completely independent peak on GPC! /.

(2-2) A type that shows a continuous peak in which the high molecular weight component (A2) and the low molecular weight component (B2) are connected by the minimum value (valley) on the GPC emission curve. From this minimum value, the high molecular weight component (A2) is the high molecular weight component and the low molecular component (B2) is the low molecular component. In many cases, the minimum value is between about 20,000 and 200,000 molecular weight.

(2-3) A type in which the high molecular weight component (A3) and the low molecular weight component (B3) show continuous peaks on the GPC emission curve and do not have a clear minimum value. In this case, with the molecular weight of 150,000 as the boundary, the high molecular weight side is the high molecular weight component (A3) and the low molecular weight side is the low molecular weight component (B3).

[0019] The high molecular weight component (A) and the low molecular weight component (B) contained in the copolymer (C) are

(2— ;!) to (2—3), which are classified and specified as (A1), (Bl), (A2 ) And (B2), or (A3) and (B3). Regardless of which method is used, the high molecular weight component (A) is defined as having a weight average molecular weight of 500,000 to 2,200,000, and the low molecular weight component (B) is defined as having a weight average molecular weight of 1,000 to 100,000; The area ratio of the molecular weight component (A) peak to the low molecular weight component (B) peak is (A) / (B) = 60/40 to 90/10.

[0020] The alkyl methacrylate having no substituent that constitutes the copolymer (C) is an alkyl methacrylate having no functional group such as a hydroxyl group or a carboxyl group (that is, an alkyl in the ester part). The group is an alkyl group without these functional groups). The alkyl group may be linear, may have a branched structure, or may have a cyclic structure. The number of carbon atoms of the alkyl group is preferably from! To 6 from the viewpoint of reactivity (polymerizability).

[0021] Specifically, as the monomer (a), methyl methacrylate, ethyl acetate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, n-pentanol Metatalylate, 2-Ethylhexylmetatalylate, n-Hexylmetatalylate, Cyclohexylmetatalylate, n-Heptylmetatalylate, n-Octylmetatalylate, Isootachinolemetatalylate, n- Nonyl methacrylate, n-decyl methacrylate, undecyl methacrylate, dodecyl methacrylate and the like can be mentioned. These may be used alone or in appropriate combination of two or more.

[0022] Without substituents! /, Alkyl acrylate (b) is an alkyl acrylate having no functional group such as a hydroxyl group or a carboxyl group (that is, the alkyl group in the ester portion has these functional groups. No alkyl group.) The alkyl group may be linear, may have a branched structure, or may have a cyclic structure. The carbon number of the alkynole group is preferably 2 to 6 because it becomes difficult to foam in the durability test after sticking.

[0023] Specifically, as monomer (b), methyl acrylate, ethyl acrylate, n-propylene acrylate, isopropyl acrylate, n-butyl acrylate, cyclohexyl acrylate, n-pentyl Atarylate, 2-ethyl hexyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, isooctyl acrylate, n-nonyl acrylate, decyl acrylate Ndecyl Atylate, Dodecyla Talirate etc. can be mentioned. These can be used alone or in appropriate combination of two or more.

[0024] Examples of the other monomer (c) having an ethylenically unsaturated double bond copolymerizable with the above (a) and (b) include the following (cl) to (c3).

(c l): A monomer having a hydroxyl group and / or a carboxyl group and having an ethylenically unsaturated double bond. Used to introduce a hydroxyl group and / or a carboxyl group into the copolymer (C).

(c2): A monomer having a substituent other than a hydroxyl group or a carboxyl group and an ethylenically unsaturated double bond.

(c3): Other monomers having an ethylenically unsaturated double bond! /, not classified as a deviation! / of the above monomers.

Monomers ( _C2 ) and (c3) are optional components.

[0025] Monomers (cl) having a hydroxyl group and an ethylenically unsaturated double bond include (meth) acrylates having a hydroxyl group in the ester moiety, such as a (meth) acrylic ester of polyol. Is preferred. Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 6-hydroxy hexyl (Meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxy decyl (meth) acrylate, 12-hydroxy laurolinole (meth) acrylate, force prolataton modified (meth) acrylates, polyethylene glycol (Meth) acrylates, polypropylene glycol (meth) acrylates and the like.

Here, “2-hydroxyethyl (meth) acrylate” is an abbreviation of “2-hydroxyethyl acrylate” and “2-hydroxyethyl methacrylate”. is there. Others are the same.

[0026] Monomers (cl) having a carboxyl group and an ethylenically unsaturated double bond include acrylic acid, methacrylic acid, / 3-carboxyethyl acrylate, itaconic acid, maleic acid, maleic anhydride, croton An acid, fumaric acid, fumaric anhydride, etc. are mentioned.

[0027] Any one of these exemplified monomers (cl) may be used, or a plurality of these monomers may be arbitrarily combined. They may be used together.

Examples of other substituents that can be used in combination with the monomer (cl) and the monomer (c2) having an ethylenically unsaturated double bond include an amino group, an amide group, a maleimide group, an itaconimide group, Examples thereof include a monomer having at least one substituent selected from the group consisting of a nucleenimide group and an epoxy group, and an ethylenically unsaturated double bond. A plurality of types of monomers (c2) can also be used in combination.

[0028] Monomers (c2) having an amino group and an ethylenically unsaturated double bond include aminomethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate. Rate, dimethylaminopropyl (meth) ate, and the like.

[0029] Examples of the monomer (c2) having an amide group and an ethylenically unsaturated double bond include (meth) acrylamide, N-substituted (meth) acrylamide, and N-butylpyrrolidone.

[0030] Examples of the monomer (c2) having a maleimide group and an ethylenically unsaturated double bond include N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide and the like. .

[0031] As the monomer (c2) having a titaconimide group and an ethylenically unsaturated double bond,

N-Methylitaconimide, N-Ethylitaconimide, N-Butylitaconimide, N-Octylitaconimide, N-2-Ethylhexylitaconimide, N-Cyclohexylitaconimide, N-Laurylitaconimide, etc. Is mentioned.

[0032] As the monomer (c2) having a nucleenimide group and an ethylenically unsaturated double bond,

N— (meth) attaroyloxymethylene nucleenimide, N— (meth) attaroyl yl 6-oxyhexamethylene nucleenimide, N— (meth) attaroyl yl 8- oxyota tamethylene nucleimide Can be mentioned.

[0033] Examples of the monomer (c2) having an epoxy group and an ethylenically unsaturated double bond include glycidyl (meth) acrylate.

[0034] The other monomers (c3) having an ethylenically unsaturated double bond!

Bulle monomers such as styrene, methylstyrene, butyltoluene, and acetic acid butyl; dibule monomers such as dibylbenzene; 14-Butyldiatalylate, i 6-Hexyldiatalylate, Hexanediol di (meth) atarylate, (Poly) ethyleneglycol di (meth) acrylate, (Poly) propylene diol Di (meth) acrylate And diatalylate monomers such as neopentyl glycol di (meth) acrylate and pentaerythritol di (meth) acrylate; and

And phosphoric acid group-containing monomers such as 2-hydroxyethyl allyloyl phosphate.

[0035] In particular, when a polyfunctional monomer such as a dibule monomer or a ditalylate monomer is used, the durability (heat resistance, heat and moisture resistance) of the formed pressure-sensitive adhesive layer is improved. I like it. However, if a polyfunctional monomer is used when obtaining the copolymer (C), gelation is likely to occur, and therefore it is preferable to use a small amount. Specifically, when the total amount of the monomers (a), (b) and (c) used for forming the copolymer (C) is 100% by weight, the compounding amount of the polyfunctional monomer is 0.00. Preferably in the range of 3% by weight.

[0036] When the total amount of the monomers (a), (b), and (c) used for the formation of the copolymer (C) is 100% by weight, as described later, under high temperature and high pressure, high temperature, high temperature high From the viewpoint of obtaining appropriate reworkability after exposure to moisture, it is important that the amount of alkylmetacrylate Ha) having no substituent is 15 35% by weight.

Further, it is important that the Tg of the copolymer (C) is 1600 ° C, and it is preferable that it is 555 ° C. When this Tg is lower than −60 ° C., the pressure-sensitive adhesive layer is liable to be lifted and foamed at high temperatures and high humidity.

[0037] Generally, the main component for forming a pressure-sensitive adhesive layer requires a force S that Tg is in the region of 0 ° C or less. In the case of a general acrylic pressure-sensitive adhesive, in order to lower the Tg of the talyl copolymer, which is the main component, an alkyl acrylate (b) ) Must be the main component. On the other hand, the alkyl methacrylate having no substituent, which is a component that raises Tg, is not used at all, or even if it is used, it is not used in a very small amount to control Tg.

[0038] Also in the present invention, in order for the Tg of the copolymer (C) to be -600 ° C, the monomer used for forming the copolymer (C) is quantitatively used. It is necessary that the alkyl acrylate (b) having no substituent is the main component. However, according to the knowledge of the present inventors, when the alkyl acrylate (b) having no substituent is too much, the flexibility of the main chain of the copolymer to be formed becomes too high. As a result, the pressure-sensitive adhesive layer formed by the reaction between such a copolymer and the curing agent (D) described later is excessively softened at high temperature or high temperature and high humidity, so that the adherend is not sensitive. It has been found that if a pressure-sensitive adhesive film is applied and exposed to a high temperature or high temperature and high humidity for a long period of time, it will be liable to float and foam.

[0039] Therefore, in the case of a general acrylic pressure-sensitive adhesive, it is not used at all, or even if it is used, it has a substituent which is not used and has a substituent which is not used at all in order to control Tg. It is characteristic and extremely important in the present invention to use 15 to 35% by weight of a non-alkyl methacrylate (ha) as compared with a conventional acrylic pressure-sensitive adhesive. In other words, the presence of the methyl group of the alkyl methacrylate without the substituent (Ha) increases the steric hindrance of the main chain of the formed copolymer (C), and the translation, vibration, and rotation of the main chain are reduced. It is suppressed. As a result, it is considered that even if a pressure-sensitive adhesive film is applied to the adherend and exposed to a high temperature or high temperature and high humidity for a long period of time, it does not float, peel off or foam.

[0040] When the alkyl methacrylate without a substituent Ha) is less than 15 parts by weight, the translation, vibration, and rotational motion of the main chain become too large, and thus it cannot withstand the harsh environment as described above. Floating and peeling, foaming and the like are likely to occur.

On the other hand, if the alkyl methacrylate without a substituent (Ha) exceeds 35% by weight, the translation, vibration and rotational movement of the main chain are excessively suppressed, and the pressure-sensitive adhesive layer becomes rigid. In this case, if the optical film as the substrate changes in size due to the harsh environment described above, the rigid pressure-sensitive adhesive layer resists the dimensional change too much, and the resistance force is around the optical film as the substrate. As a result, the light leakage phenomenon occurs at the peripheral edge.

[0041] The copolymer (C) needs to have a hydroxyl group and / or a carboxyl group as a functional group for reacting with the isocyanate curing agent (D) described later. The amount of the monomer (cl) having a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated double bond used for introducing a hydroxyl group or a carboxyl group constitutes the copolymer (C). Of the total 100% by weight of the monomer to be used, 0.01 to 10% is preferable. 0.05 to 8% % Is more preferable. When this monomer (cl) is less than 0.01% by weight, the cohesive force as a pressure-sensitive adhesive layer is insufficient, and the pressure-sensitive adhesive film is not easily lifted or peeled off at high temperature or high humidity. It tends to occur. On the other hand, if the monomer (cl) force exceeds 0% by weight, the degree of crosslinking becomes too high and pressure-sensitive adhesiveness (tackiness) becomes poor, which is not preferable.

[0042] As described above, the amount of alkyl methacrylate (ha) having no substituent, the amount of monomer (cl) having a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated double bond, In consideration of the Tg of the copolymer (C) and the amount of monomers other than (a) and (c 1) used for the formation of the copolymer (C), that is, alkyl having no substituent Atallate (b), a monomer having a substituent other than a hydroxyl group or a carboxyl group and an ethylenically unsaturated double bond (c2), and an ethylenically unsaturated double bond not classified as any of the above monomers The amount of the other monomer (c3) having can be appropriately selected.

For example, the alkyl acrylate (b) having no substituent is preferably 45% by weight or more, more preferably 50 to 78% by weight.

[0043] The copolymer (C) contains two copolymer components, a high molecular weight component (A) and a low molecular weight component (B) as described above. These two copolymer components are divided into the following three types according to the peak shape of the GPC emission curve.

That is, (2-1) When copolymer (C) has a completely independent peak on the GPC emission curve, copolymer (C) has a high molecular weight component (A1) And (A1) and (B1) are contained with the low molecular weight side as the low molecular weight component (B1).

(2-2) Copolymer (C) has a continuous peak on the GPC emission curve, with a minimum value (valley), specifically a minimum value between about 20,000 and 200,000 in molecular weight. In the case of having the copolymer (C), the high molecular weight component is defined as the high molecular weight component (A2) and the low molecular weight component is defined as the low molecular weight component (B2). Contains B2).

(2-3) If the copolymer (C) does not have a clear minimum between about 20,000 and 200,000 in the GPC emission curve, the copolymer (C) has a molecular weight of 150,000. As a boundary, a copolymer composed of polymer molecules having a molecular weight of 150,000 or more is defined as a high molecular weight component (A3), and a copolymer component composed of polymer molecules having a molecular weight of less than 150,000 is defined as a low molecular weight component (B3). Contains A3) and (B3). [0044] The weight average molecular weights of the high molecular weight components (Al), (A2), and (A3) specified as described above are 500,000 to 2,200,000, and preferably 700,000 to 2,000,000. . The weight average molecular weights of the low molecular weight components (Bl), (B2), and (B3) specified as described above are 1000 to 100,000, preferably 5,000 to 80,000.

If the weight average molecular weight of the high molecular weight component (A) is less than 500,000, the cohesive force of the pressure-sensitive adhesive layer will be insufficient even when reacted with the isocyanate curing agent (D) described later, causing floating and peeling, foaming, etc. Occurs. On the other hand, when the weight average molecular weight of the high molecular weight component (A) is larger than 2.2 million, the viscosity becomes high and the workability such as coating becomes inferior, and the optical properties cannot be maintained.

On the other hand, when a low molecular weight component (B) having a weight average molecular weight of less than 1000 is used, the cohesive force is insufficient, and it tends to float, peel off, and foam. In addition, if a low molecular weight component (B) having a weight average molecular weight exceeding 100,000 is used, the stress concentration resulting from the expansion and contraction of the film cannot be sufficiently absorbed and relaxed, and a light leakage phenomenon occurs.

[0045] Furthermore, the peak area ratio in GPC of the high molecular weight components (Al), (A2), (A3) and the low molecular weight components (Bl), (B2), (B3) is (Α1) / (/ 1 ) = Force that is 60/40 to 90/10, or (A2) / (B2) = force that is 60/40 to 90/10, or (A3) / (B3) = 60 / 40—9 It is important that the ratio is 0/10, preferably 65/35 to 85/15. If the proportion of the low molecular weight component (B) is too small, the stress concentration caused by the expansion and contraction of the optical film cannot be sufficiently absorbed or relaxed, and a light leakage phenomenon occurs. On the other hand, if the proportion of the low molecular weight component (B) is too large, the cohesive force of the pressure-sensitive adhesive layer is insufficient, and it is likely to float and peel off, resulting in foaming.

In addition, it contains a high molecular weight component (8) and a low molecular weight component (8) at a ratio of 60/40 to 90/10, so that the adhesive layer has good reworkability even after being subjected to harsh conditions. The power S to obtain

[0046] Such a copolymer (C) can be obtained by various methods. For example, the high molecular weight component (A) and the low molecular weight component (B) can be obtained separately and mixed together, or the high molecular weight component (i.e., the above (Al) to (A3 A high-molecular-weight component comprising a high-molecular-weight component), and a low-molecular-weight component obtained by polymerizing the monomer in the presence of the obtained copolymer. To obtain a copolymer (C) as it can.

From the viewpoint of maintaining optical properties at high temperature or high temperature and high humidity, the latter method is more preferable.

[0047] In the following, after obtaining a high molecular weight component (first stage polymerization), which is a more preferred method, the monomer is polymerized (second stage polymerization) in the presence of the obtained high molecular weight component. The method for obtaining the low molecular weight component will be described in more detail.

For example, the high molecular weight component is 0.0;! To 1 part by weight of a polymerization initiator, more preferably 100 parts by weight of the monomers (a) to (c) used in the first stage, It is obtained by a method such as bulk polymerization or solution polymerization, preferably solution polymerization, using a polymerization initiator of 0.01 to 0.1.

[0048] As the polymerization initiator, an azo compound or an organic peroxide is used, and two or more polymerization initiators may be used in combination.

In the case of solution polymerization, polymerization solvents include methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, hexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n propanol, isopropanol, etc. Is used. Two or more polymerization solvents can be mixed and used.

[0049] Among the polymerization initiators, examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1, 1'-azobis. (Cyclohexane 1 carbonitryl), 2, 2 'azobis (2, 4 dimethylvaleronitrile), 2, 2' azobis (2, 4 dimethyl-4-methoxyvaleronitryl), dimethyl 2, 2 'azobis (2 methyl) Norepropionate), 4, 4'-azobis (4 cyanovaleric acid), 2, 2 'azobis (2-hydroxymethylpropionitrile), 2, 2'-azobis (2- (2-imidazoline-2-i) E) Propane) and the like.

[0050] Examples of the organic peroxide include benzoyl peroxide, t-butyl perbenzoate, tamen hydroperoxide, diisopropyl peroxydicarbonate, di-n-propylenoperoxydicarbonate, di (2— Etoxyshettinore) peroxydicarbonate, tert-butenoreperoxyneodecanoate, tert-butenoreperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionylperoxide, diacetylperper An oxide etc. are mentioned.

[0051] First, it is preferable to polymerize the monomers (a) to (c) until the polymerization conversion is 60 to 90% by controlling the blending amount of the polymerization initiator as described above. By this first stage polymerization, a copolymer constituting the high molecular weight component (A) of the copolymer (C) can be first obtained in the system. The copolymer obtained by the first-stage polymerization mainly comprises the high molecular weight component (A), but may contain other copolymer components.

Here, the polymerization conversion rate is a value obtained by dividing the weight of the copolymer obtained by polymerizing the monomer by the total weight of the monomers used as raw materials. More specifically, a very small amount of the solution during polymerization is sampled and heated at 150 ° C for about 20 minutes to obtain the solid content. The monomer volatilizes under the heating conditions, but the copolymer does not volatilize. Therefore, by determining the solid content of the solution, the amount of the copolymer contained can be determined, and the polymerization conversion rate is calculated based on that.

[0052] In the next! /, If necessary, the new monomer (a) to (c) and / or the polymerization initiator is removed, and the second stage polymerization is carried out in the system after the first stage polymerization. The remaining monomer (and a new monomer added if necessary) is further radically polymerized to form a low molecular weight component (Β). Thus, the force S can be obtained to obtain a copolymer (C) containing a high molecular weight component (Α) and a low molecular weight component (Β).

The polymerization conversion rate of the copolymer (C) in the second stage polymerization is 80 to 100%, preferably 90 to 100%, more preferably 95 to 100%. More preferably. That is, out of the total 100% by weight of the monomers used in the polymerization, including the monomers added as necessary in the second stage polymerization process, the monomers remaining in the reaction system are preferred. Is copolymerized by forming a low molecular weight component by radical copolymerization until it is less than 20% by weight, more preferably less than 10% by weight, and even more preferably less than 5% by weight. C) can be obtained.

[0053] In this second stage polymerization, a monomer (c) having a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated double bond is preferred, even though it is preferable to add a new monomer (c). It is more preferable to add cl). As described above, the monomer (cl) is 0% in total of 100% by weight of all monomers used for the polymerization of the high molecular weight component (A) and the low molecular weight component (B). 01 to 10% by weight is preferred. 0.05 to 8% by weight is more preferred. Of these, the amount of monomer (cl) used in the first stage polymerization is preferably 0.008 to 8% by weight, preferably 0.04 to 6% by weight. More preferably, the amount of monomer (c2) newly added during the second stage polymerization is preferably 0.002 to 2% by weight 0.0;! To 2% by weight It is more preferable that Pressure sensitive adhesive from the end when optical film is cut by adding monomer (cl) and actively introducing hydroxyl and / or carboxyl groups into low molecular weight component (B) This is effective in preventing the protrusion of spills.

[0054] When forming the low molecular weight component (B) in the second stage polymerization, the polymerization initiator used in the first stage is more than the polymerization initiator used in the first stage. It is preferable to use about 5 to 50 times the amount of the polymerization initiator. More specifically, 0.05 to 50 parts by weight of the polymerization initiator, more preferably 0. 5 parts by weight with respect to 100 parts by weight of the total of the monomers (a) to (c) used in the second stage. It is preferable to use 05 to 5 parts by weight of a polymerization initiator.

Furthermore, in order to control the molecular weight to the low molecular weight side, a chain transfer agent such as n-lauryl mercaptan or n-dodecyl mercaptan, α-methylstyrene dimer or limonene is used for the synthesis of the low molecular weight component (B). May be.

In this way, GPC! /, A copolymer having a high molecular weight component (Α) and a low molecular weight component (Β) having an area ratio of (Α) / (Β) = 60/40 to 90/10 (C) can be preferably obtained.

[0055] The ability to obtain a pressure-sensitive adhesive by mixing the copolymer (C) having a hydroxyl group and / or a carboxyl group obtained as described above and an isocyanate curing agent (D). S can. The isocyanate curing agent (D) reacts with the hydroxyl group and / or carboxyl group of the copolymer (C) when forming a pressure-sensitive adhesive film to form a pressure-sensitive adhesive layer.

Upon mixing, the copolymer (C) is preferably in a solution state dissolved in an organic solvent.

[0056] As the isocyanate curing agent (D), those having two or more isocyanate groups in one molecule are preferable, and those having 2 to 4 are more preferable.

By using the isocyanate curing agent (D), a stable pressure-sensitive adhesive property can be obtained, and the adhesiveness to the base material is reduced, so that it is a useful curing agent. [0057] Examples of the isocyanate curing agent (D) include: toxylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane dianocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate. , Polyisocyanate compounds such as polymethylenpolyphenyl isocyanate;

Adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane;

Examples include burettes or isocyanurates of these polyisocyanate compounds; and adducts of these polyisocyanate compounds with known polyether polyols or polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, and the like. These can be used alone or in any combination of two or more! /.

The isocyanate curing agent (D) is preferably used in an amount of 0.01 to 15 parts by weight with respect to 100 parts by weight of the copolymer (C). If the amount is less than 01 parts by weight, the cohesive force of the pressure-sensitive adhesive layer decreases, and if it exceeds 15 parts by weight immediately, the pressure-sensitive adhesiveness to the adherend becomes poor. More preferably, 0.03 to 10 parts by weight, and particularly preferably 0.05 to 2 parts by weight.

[0058] The pressure-sensitive adhesive contains at least one curing agent other than the isocyanate curing agent (D), for example, an epoxy curing agent, an ethyleneimine curing agent, a metal chelate curing agent, and an amine curing agent. It can be used in combination with an isocyanate curing agent (D). When blending a curing agent other than these isocyanate curing agents (D), the blending amount is preferably 0.0;! To 8 parts by weight per 100 parts by weight of the copolymer (C).

[0059] Examples of the epoxy curing agent include bisphenol A-epoxychlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidino enoate, glycerin diglycidino enotenole, glycerin ligine Ginole etherol, 1,6 monohexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl dilin, N, N, Ν ', Ν'-tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N, monodiglycidinoleaminomethinole) cyclohexane, N, N, Ν ', Ν'— Examples include tetraglycidylaminophenyl methane.

[0060] Examples of the ethyleneimine curing agent include N, N, -diphenylmethane 4, 4'-bis (1 aziridine canolepoxysite), N, N'-tonolene 2, 4-bis (1 aziridine) Canorepoxite), bisisophthalloy 1 (2-methylaziridine), tree 1 aziridinyl phosphate oxide, N, N 'hexamethylene 1, 6-bis (1-aziridinecarboxite), 2, 2, 1-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], trimethylolpropane tri-β-aziridinylpropionate, tetramethylol methanetree / 3-aziridinylpropionate, Tris-2, 4, 6- (1 aziridinyl) -1,3,5-triazine and the like.

[0061] Examples of the metal chelate curing agent include aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium, and acetylacetone or acetoacetic acid. And a coordination compound with ethyl.

[0062] Further, examples of amine curing agents include hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethyltetramine, isophoronediamine. And amino resins and methylene resins.

[0063] The pressure-sensitive adhesive preferably further contains a silane coupling agent.

Examples of silane coupling agents include butyltrimethoxysilane, butyltriethoxysilane,

Xysilane, _グリ_{-glycidoxypropino} methino _lesoxysilane , 2- (3,4 epoxy epoxyaminopropyltriethoxysilane, γ-aminopropylmethylmethoxysilane, Ν- (2-aminoethyl) 3 aminopropyl Examples include trimethoxysilane, Ν- (2 aminoethyl) 3 aminopropropyltriethoxysilane, mercaptobutyltrimethoxysilane, γ-mercaptopropinolemethyldimethoxysilane, etc. These may be used in combination of two or more. .

Silane coupling agents are effective in improving the adhesion between pressure-sensitive adhesive layers and glass, This is particularly effective for preventing the pressure-sensitive adhesive film from floating and peeling off and foaming under high humidity.

[0064] The content of the silane coupling agent in the pressure-sensitive adhesive is preferably 0.0;! 2 parts by weight with respect to 100 parts by weight of the copolymer (C). If the amount is less than 01 parts by weight, the effect of improving the physical properties is insufficient. If the amount exceeds 2 parts by weight, the pressure-sensitive adhesive is not only expensive, but also may cause floating and peeling, foaming, etc. There is.

[0065] Further, the pressure-sensitive adhesive does not inhibit the effect of the present invention! /, As far as it is concerned, an ultraviolet absorber, an antioxidant, a pressure-sensitive adhesive resin, a plasticizer, an antifoaming agent, and a leveling agent. One or more known additives such as a regulator may be optionally blended.

[0066] By using the pressure-sensitive adhesive according to the present invention, the adhesiveness to the optical film is good, and after the optical film is attached to the adherend, it is long under high temperature and high pressure, high temperature or high temperature and high humidity. Even if it is exposed for a period of time, it is possible to form a pressure-sensitive adhesive layer that does not cause foaming at the sticking interface, does not float or peel off, and has excellent reworkability as well as no light leakage phenomenon.

Next, a pressure-sensitive adhesive film obtained using the pressure-sensitive adhesive will be described. In this pressure-sensitive adhesive film, a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive is used for various display members. The pressure-sensitive adhesive film that is formed on at least one surface of the optical film is suitably used for forming various display members, for example, suitably pasted and used on the glass of a liquid crystal display member. The

Examples of the optical film include a polarizing film and a retardation film, and a polarizing film is preferable.

[0068] The pressure-sensitive adhesive film can be formed by applying a pressure-sensitive adhesive to the surface of the optical film and drying to form a pressure-sensitive adhesive layer. Preferably, a release sheet is laminated on the obtained pressure-sensitive adhesive layer. If necessary, the adhesive layer may be aged. Alternatively, the pressure-sensitive adhesive layer on the optical film can be formed by applying a pressure-sensitive adhesive to the release sheet, drying to form a pressure-sensitive adhesive layer, and then bonding it to the optical film, The so-called "transfer method" that transfers the pressure-sensitive adhesive layer on the optical film According to that.

[0069] The pressure-sensitive adhesive layer can be formed using a commonly used coating apparatus. Examples of the coating apparatus include a roll knife coater, a die coater, a roll coater, a no coater, a gravure rhino recoater, a reno-kuno slow coater, a datebing, and a blade coater.

The thickness of the pressure-sensitive adhesive layer (after drying) is preferably; If it is less than m, pressure-sensitive adhesiveness may be poor, and if it exceeds 200 m, it may be difficult to produce and handle a pressure-sensitive adhesive film.

[0070] pressure-sensitive adhesive layer obtained as described above is preferably a storage modulus force ^{0. 01 X 10 5 Pa~5 X 10} 5 Pa at 25 ° C. More preferably, it is 0.05 x 10 ^{5 to} 3 x 10 ⁵ . The storage elastic modulus can be measured by using a viscoelasticity tester “RDA-III” manufactured by TA Instruments Japan.

[0071] When the storage elastic modulus at 25 ° C of the pressure-sensitive adhesive layer is less than 0.01 X 10 ⁵ Pa, after bonding to an adherend such as glass, the pressure sensitive adhesive layer is long under high temperature or high humidity. When exposed for a period of time, the pressure-sensitive adhesive layer may be softened, and may be easily lifted, peeled off, or foamed. On the other hand, if the storage elastic modulus of the pressure-sensitive adhesive layer at 25 ° C is greater than ⁵ × 10 ⁵ Pa, the heat resistance is sufficiently high. The pressure-sensitive adhesive layer is hard at room temperature, so the pressure-sensitive adhesive layer When laminating an adhesive film, the pressure-sensitive adhesive layer does not sufficiently adhere to the adherend, and the pressure-sensitive adhesive force tends to decrease.

Example

Next, the present invention will be described in further detail with reference to examples, but the present invention is not limited thereto. In the examples, “part” means “part by weight” and “%” means “% by weight”.

In the following production examples and comparative production examples, for convenience, a copolymer component having a weight average molecular weight of 100,000 or more is referred to as “high molecular weight component (A)”, and a copolymer component having a weight average molecular weight of less than 100,000 is referred to as “low and high. The molecular weight component (B) ”was assigned a sequential number. In addition, the copolymer was numbered consecutively as “C” regardless of whether it was an embodiment of the present invention.

[0073] <Production example 1> In a reaction vessel (hereinafter simply referred to as “reaction vessel”) equipped with a stirrer, thermometer, reflux condenser, dropping device, and nitrogen inlet tube, 76 parts of n-butyl acrylate and 22 parts of methyl metatalylate 1 · 5 parts of attalinoleic acid, 100 parts of acetone, ΑΙΒΝ (2, 2'-azobisisobutyronitrile, hereinafter referred to as “AIBN”) 0. 03 parts are charged, and the air in the reaction vessel is filled with nitrogen. Replaced with gas. Then, while stirring under a nitrogen atmosphere, this reaction solution is reacted at a reflux temperature for 4.5 hours until the conversion becomes 75%, and a mixed solution of a copolymer having a weight average molecular weight of 1,000,000 and a monomer is obtained. Got. Next, 200 parts of tonoleene, 0.5 part of acrylic acid and 0.2 part of AIBN were added, and the mixture was further reacted for 6 hours until the conversion reached 100%. Copolymer (C1) with a Tg of 29.4 ° C Solution was obtained.

[0074] The copolymer (C1) does not contain a polymer having a molecular weight of less than 150,000, has a weight average molecular weight of 1 million, a high molecular weight component (A1-1) having a Tg of -29.9 ° C, a molecular weight of 15 It contained no more than ten thousand polymers and contained a low molecular weight component (B1-1) having a weight average molecular weight of 30,000 and a Tg of -28 ° C. The high molecular weight component (A1-1) and the low molecular weight component (B1-1) show two independent peaks in the GPC emission curve, and the area ratio between them is (A1-1-1) / (B1-1) 1) = 75/25.

[0075] The Tg of the high molecular weight component (A1-1) is based on the glass transition temperature of the homopolymer obtained from each monomer, assuming that each monomer used is uniformly polymerized. The value obtained from the following equation (1). The Tg of the low molecular weight component (B1-1) is based on the unreacted remaining monomer, the amount of each added monomer, and the glass transition temperature of the homopolymer obtained from each monomer. The value obtained by the following equation (1). The Tg of the copolymer (C1) is expressed by the following formula (based on the glass transition temperature of the homopolymer obtained from each monomer constituting the copolymer (C1) (that is, the blended monomer): The value obtained by 1).

Formula (1) (FOX formula):

1 / Tg = [(Wl / Tgl) + (W2 / Tg2) + ... + (Wn / Tgn)]

/ 100 (where temperature is absolute)

Wn:% by weight of monomer n

Tgn: Glass transition temperature of homopolymer consisting of monomer n

<Production Example 2> In a reaction vessel, 73-98 parts of n-butyl acrylate, 24 parts of n-butinomethacrylate, 1.5 parts of attalic acid, light acrylate 4EG-A (PEG # 200 diatalylate, manufactured by Kyoeisha Chemical Co., Ltd.) The same shall apply hereinafter.) 0.02 part, 100 parts of acetone, and 03 parts of AIBNO. 03 parts were prepared and reacted in the same manner as in Production Example 1 for 4.5 hours until the conversion reached 75%. The weight average molecular weight was 980,000. A mixed solution of a polymer and a monomer was obtained.

Next, 200 parts of tonoleene, 0.5 part of atalinoleic acid and 0.2 part of ΑΙΒΝ are added, and the mixture is further reacted for 6 hours until the conversion rate reaches 100%. Copolymer (C2) having a Tg of -37.8 ° C Got a solution of

Yes

[0077] The copolymer (C2) does not contain a polymer having a molecular weight of less than 150,000, has a weight average molecular weight of 980,000, a Tg of -38.2 ° C, a high molecular weight component (A1-2), and a molecular weight of 15 It contained no more than 10,000 polymers and contained a low molecular weight component (B1-2) with a weight average molecular weight of 31,000 and a Tg of -36.4 ° C. The high molecular weight component (A1-2) and the low molecular weight component (B1-2) show two independent peaks in the GPC emission curve, and the area ratio between them is (Al-2) / (Β1 — 2) = 75/25.

Note that Tg was determined by excluding the light amount of light acrylate 4EG-A.

[0078] <Production Example 3>

A reaction vessel was charged with 74 parts of n-butyl acrylate, 24 parts of methyl methacrylate, 1 · 5 parts of acrylic acid, 100 parts of acetone, 0.03 parts of AIBN, and the conversion rate was 65% as in Production Example 1. The reaction was allowed to proceed for 4 hours until a mixture solution of a copolymer having a weight average molecular weight of 1,010,000 and a monomer was obtained.

Next, 200 parts of tonoleene, 0.5 part of 2-hydroxyethyl methacrylate and 0.2 part of AIBN were added and reacted for another 6 hours until the conversion reached 100%. A solution of copolymer (C3) was obtained.

[0079] Copolymer (C3) does not contain a polymer with a molecular weight of less than 150,000, has a weight average molecular weight of 1010,000, a Tg of -27.6 ° C, a high molecular weight component (A1-3), and a molecular weight of 15 It contained no more than 10,000 polymers and contained a low molecular weight component (B1-3) having a weight average molecular weight of 28,000 and a Tg of −26.3 ° C. The high molecular weight component (A1-3) and the low molecular weight component (B1-3) show two independent peaks in the GPC emission curve, and the area ratio between them is (Al-3) / (Β1-3 ) = 6 It was 5/35.

[0080] <Production example 4>

A reaction vessel was charged with 83 parts of n-butyl acrylate, 15 parts of methyl methacrylate, 1 · 5 parts of acrylic acid, 100 parts of acetone and 03 parts of AIBNO. The reaction was allowed to proceed for 5 hours until a mixture solution of a copolymer having a weight average molecular weight of 1 million and a monomer was obtained.

Next, 200 parts of tonoleene, 0.5 part of attalinoleic acid, and 0.2 part of タ are added, and the reaction is further continued for 6 hours until the conversion reaches 100%. Copolymer (C4) having a Tg of -37.1 ° C Got a solution of

Yes

[0081] The copolymer (C4) does not contain a polymer having a molecular weight of less than 150,000, has a weight average molecular weight of 1 million, a Tg of -37.6 ° C, a high molecular weight component (A1-4), and a molecular weight of 15 It contained no more than ten thousand polymers and contained a low molecular weight component (B1-4) with a weight average molecular weight of 37,000 and a Tg of -35.8 ° C. The high molecular weight component (A1-4) and the low molecular weight component (B1-4) show two independent peaks in the GPC emission curve, and the area ratio between them is (Al-4) / (Β1-4) ) = 8 5/15.

The monomer yarns were n-fu, chinore accreta 卜 82. methinomethacrylate 15 2, 2-hydroxyxetyl metatalylate 1 · 5 parts, light acrylate 4EG— A 0.02 parts. Except for the above, the reaction was carried out in the same manner as in Production Example 2 until the conversion rate reached 75% to obtain a mixed solution of a copolymer having a weight average molecular weight of 1,000,000 and a monomer.

Next, the reaction was conducted until the conversion reached 100% in the same manner as in Production Example 2, except that 0.5 part of 2-hydroxyethyl methacrylate was added instead of 0.5 part of acrylic acid. A solution of copolymer (C5) at 37 ° C was obtained.

[0083] The copolymer (C5) does not contain a polymer having a molecular weight of less than 150,000, has a weight average molecular weight of 1 million, a high molecular weight component (A1-5) having a Tg of -37.9 ° C, a molecular weight of 15 It contained no more than 10,000 polymers, and contained a low molecular weight component (B1-5) having a weight average molecular weight of 31,000 and a Tg of -35.6 ° C. The high molecular weight component (A1-5) and the low molecular weight component (B1-5) show two independent peaks in the GPC emission curve, and the area ratio between them is (Al-5) / (Β1— Five) = 75/25.

A reaction vessel was charged with 78 parts of n-butyl acrylate, 20 parts of methyl methacrylate, 2 parts of acrylic acid, 100 parts of acetone, and 03 parts of AIBNO. 03, and the air in the reaction container was replaced with nitrogen gas. Then, while stirring in a nitrogen atmosphere, this reaction solution is reacted for 6 hours at a reflux temperature until the conversion rate reaches 100%, and does not contain a component having a weight average molecular weight of 1,050,000 and a molecular weight of less than 150,000, Tg 31. A solution of high molecular weight copolymer (A1-6) at 7 ° C was obtained. The obtained copolymer solution was diluted with toluene to adjust the nonvolatile content concentration to 40%.

[0085] In a separate reaction vessel, 78 parts of n-butinorea tallylate, 20 parts of methinoremethalate, 2 parts of acrylic acid, 150 parts of toluene, and 0.03 part of AIBN were charged, and the air in this reaction vessel was nitrogenated. Replaced with gas. Then, while stirring under a nitrogen atmosphere, this reaction solution is reacted at reflux temperature for 6 hours until the conversion becomes 100%, Tg is -31.7 ° C, weight average molecular weight is 30,000, molecular weight is more than 150,000. Thus, a solution of a low molecular weight copolymer (B1-6) not containing the above component was obtained (nonvolatile content concentration: 40%).

[0086] Next, the weight specific force S between the high molecular weight component (A1-6) and the low molecular weight component (B1-6) S, (A1-6) / (Β1-6) = 75/25 The polymer solution was mixed to obtain a copolymer (C6) solution having a Tg of −31 · 7 ° C., and GPC was measured. The area ratio of the high molecular weight component (A1-6) to the low molecular weight component (B1-6) was (A1-6) / (B1-6) = 75/25.

In a reaction vessel, n-p, chinorethalate 67 · methinolemethacrylate 30 咅 ^ 2-hydroxychichetylmethacrylate 2 parts, light acrylate 4EG— A 0.02 parts, acetone 110 parts, AIBN0 In the same manner as in Production Example 6, charge 03 parts and let react for 6 hours until the conversion rate reaches 100%. Do not contain any components with a weight average molecular weight of 1.05 million and a molecular weight of less than 150,000, Tg-19.9 A solution of high molecular weight copolymer (A1-7) at ° C was obtained. The obtained copolymer solution was diluted with toluene to adjust the nonvolatile content concentration to 40%.

[0088] In a separate reaction vessel, 67.98 parts of n-butinorea tallylate, 30 parts of methinoremethalate, acrylolic acid, lyreatareata 4EG—A 0.0.2, 卜 noren 130, AIBNO. 03¾¾ In the same manner as in Preparation Example 6, the reaction was allowed to proceed for 6 hours until the conversion rate reached 100%, and the Tg was -19.9 ° C, the weight average molecular weight was 30,000, the molecular weight was not more than 150,000, and the content was low. A solution of the molecular weight copolymer (B1-7) was obtained (nonvolatile content concentration: 40%).

[0089] Next! /, So that the weight ratio of high molecular weight component (A1-7) to low molecular weight component (B1-7) is (A1-7) / () 1-7) = 90/10 The two copolymer solutions were mixed with each other to obtain a copolymer (C6) solution having a Tg of −19.9 ° C., and GPC was measured. The area ratio of the high molecular weight component (A1-7) to the low molecular weight component (B1-7) was (A1-7) / (B1 7) = 90/10.

Monomer yarns are made with n,, and chinole acreole 卜 82. methinoremethacrylate 卜 15, 2 hydrochetyl methacrylate 1 · 5 parts, light acrylate 4EG— A 0.02 parts In the same manner as in Production Example 2, the reaction was carried out until the conversion rate reached 75% to obtain a mixed solution of a copolymer and a monomer having a weight average molecular weight of 980,000.

Next, 150 parts of ethyl acetate, 50 parts of tonoleene, 0.5 part of 2-hydroxyethyl methacrylate and 0.2 part of AIBN were added and reacted for another 6 hours until the conversion reached 100%. A solution of C copolymer (C8) was obtained.

[0091] Copolymer (C8) shows a continuous peak having a minimum value at a molecular weight of 120,000 in GPC, a high molecular weight component (A2-8) on the higher molecular weight side than this minimum value, Also contains a low molecular weight component (B2-8) on the low molecular weight side, the weight average molecular weight of the high molecular weight component (A2-8) is 1 million, and the weight average molecular weight of the low molecular weight component (B2 8) is The area ratio between them was (A2−8) / (B2−8) = 75/25.

[0092] <Production Example 9>

Monomer yarns are made with n,, and chinole acreole 卜 82. methinoremethacrylate 卜 15, 2 hydrochetyl methacrylate 1 · 5 parts, light acrylate 4EG— A 0.02 parts In the same manner as in Production Example 2, the reaction was carried out until the conversion rate reached 75% to obtain a mixed solution of a copolymer and a monomer having a weight average molecular weight of 950,000.

Next, 200 parts of ethyl acetate, 0.5 part of 2-hydroxyethyl methacrylate and 0.2 part of AIBN were added, and the mixture was further reacted for 6 hours until the conversion reached 100%. A solution of coalescence (C9) was obtained.

[0093] Copolymer (C9) shows a continuous peak having no clear minimum value in GPC, a high molecular weight component (A3-9) having a molecular weight of 150,000 or more, and a molecular weight of less than 150,000. Low molecular weight component (B3-9), the high molecular weight component (A3-9) has a weight average molecular weight of 1,000,000, and the low molecular weight component (B3-9) has a weight average molecular weight of 80,000. The ratio was (A3−9) / (B3−9) = 75/25.

[0094] <Comparative Production Example 1>

In the same manner as in Production Example 1 except that the monomer composition was 99 parts of n-butinorea tallylate, 1 part of 4-hydroxybutyl acrylate, and 75 parts of acetone, the reaction was carried out until the conversion reached 75%. A mixed solution of a copolymer having a weight average molecular weight of 1.6 million and a monomer was obtained.

Next, 200 parts of tonoleene, 0.25 part of atolinoleic acid and 0.2 part of AIBN were added, and the mixture was further reacted until the conversion reached 100% in the same manner as in Production Example 1, with a Tg of -54.1 ° C. A solution of the copolymer (C10) was obtained.

[0095] The copolymer (CC10) does not contain a polymer having a molecular weight of less than 150,000, has a weight average molecular weight of 1600,000, a Tg of -54.3 ° C, a high molecular weight component (A1-10), and a molecular weight It contained no more than 150,000 polymers and had a low molecular weight component (B1-10) with a weight average molecular weight of 34,000 and a Tg of -53.4 ° C. The high molecular weight component (A1-10) and the low molecular weight component (B1-10) show two independent peaks in the GPC emission curve, and the area ratio between them is (Al-5) / (B 1- 5) = 75/25.

[0096] <Comparative Production Example 2>

React until the conversion reaches 75% in the same manner as in Production Example 1 except that the monomer composition is 58 parts of n-butinorea tallylate, 40 parts of methinoremethalate, and 1.5 parts of acrylic acid. Thus, a mixed solution of a copolymer having a weight average molecular weight of 1 million and a monomer was obtained.

Next, 200 parts of tonoleene, 0.5 parts of atalinoleic acid, and 0.2 parts of タ are added and further reacted in the same manner as in Production Example 1 until the conversion becomes 100%. A solution of coalescence (C11) was obtained.

[0097] The copolymer (C11) does not contain a polymer having a molecular weight of less than 150,000, has a weight average molecular weight of 100,000, a Tg of 7.4 ° C, a high molecular weight component (A1-11), and a molecular weight. Contains over 150,000 polymers And a low molecular weight component (B1-11) having a weight average molecular weight of 25,000 and a Tg of -5.8 ° C. The high molecular weight component (A1-11) and the low molecular weight component (B1-11) show two independent peaks in the GPC emission curve, and the area ratio between them is (Al-11) / (B1-1-11). ) = 75/25.

[0098] <Comparative Production Example 3>

The same as in Production Example 1 except that the monomer composition was 76 parts of n-butinorea tallylate, 22 parts of methinoremethalate, and 1.5 parts of acrylic acid. The mixture was reacted for 4 hours to obtain a mixed solution of a copolymer and a monomer having a weight average molecular weight of 1,040,000.

Next, 200 parts of tonoleene, 0.5 part of atalinoleic acid, and 0.2 part of リ are added, and in the same manner as in Production Example 1, the reaction is further continued until the conversion becomes 100%, and the Tg is −32.4 ° C. A solution of the copolymer (C12) was obtained.

[0099] The copolymer (C12) does not contain a polymer having a molecular weight of less than 150,000, has a weight average molecular weight of 104,000, a Tg of -32.1 ° C and a high molecular weight component (A1-12), It contained no polymer with a molecular weight of 150,000 or more, and contained a low molecular weight component (B1-12) having a weight average molecular weight of 30,000 and a Tg of -32.9 ° C. The high molecular weight component (A1-12) and the low molecular weight component (B1-12) show two independent peaks in the GPC emission curve, and the area ratio between them is (Al-12) / (B1 — 12) = 58/42.

[0100] <Comparative Production Example 4>

The same as in Production Example 1 except that the monomer composition was 76 parts of n-butinorea tallylate, 22 parts of methinoremethalate, and 1.5 parts of acrylic acid. Reaction was performed for 5 hours to obtain a mixed solution of a copolymer and a monomer having a weight average molecular weight of 1.1 million.

Next, 200 parts of tonoleene, 0.5 part of atalinoleic acid, and 0.2 part of リ are added, and in the same manner as in Production Example 1, the reaction is further continued until the conversion becomes 100%, and the Tg is −32.4 ° C. A solution of the copolymer (C13) was obtained.

[0101] Copolymer (C13) does not contain a polymer with a molecular weight of less than 150,000, has a weight average molecular weight of 11,000,000, a Tg of 32.1 ° C, a high molecular weight component (A1-13), It contained no more than 150,000 polymers and contained a low molecular weight component (B1-13) with a weight average molecular weight of 28,000 and a Tg of -34.9 ° C. The high molecular weight component (A1-13) and the low molecular weight component (B1-13) The emission curve showed two independent peaks, and the area ratio between them was (A1-13) / (B1-13) = 90/10.

[0102] <Comparative Production Example 5>

The conversion rate is 75% in the same manner as in Production Example 1, except that the monomer yarn is made of 76 parts of n-butenorea talelate, 22 parts of methinoremethalate, and 1.5 parts of attalinoleic acid. The mixture was reacted for 4.5 hours until a mixed solution of copolymer and monomer having a weight average molecular weight of 1 million was obtained.

Next, 50 parts of acetone, 150 parts of toluene, and 0.5 part of acrylic acid were added, and the reaction was further continued until the conversion reached 100% in the same manner as in Production Example 1, and the Tg was -32.4 ° C. A solution of copolymer (C14) was obtained.

[0103] Copolymer (C14) shows a continuous peak having a minimum value at a molecular weight of 180,000 in GPC, a high molecular weight component (A2-14) on the higher molecular weight side than this minimum value, and a minimum value. It contains a low molecular weight component (B2-14) on the low molecular weight side. The weight average molecular weight of the high molecular weight component (A2-14) is 1 million, the weight average molecular weight of the low molecular weight component (B2-14) is 120,000, and the area ratio of both is (A2-14) / (B2-14) = It was 75/25.

Manufactured except that the monomer yarn is composed of 76 parts of n-butenorea tallylate, 22 parts of methenoremethalate, 1.5 parts of attalinoleic acid, 75 parts of toluene, 25 parts of acetone and 0.03 parts of AIBN. In the same manner as in Example 1, the reaction was carried out until the conversion rate reached 75% to obtain a mixed solution of a copolymer and a monomer having a weight average molecular weight of 450,000 and Tg of -32.1 ° C.

Next, 200 parts of tonoleene, 0.5 part of atalinoleic acid, and 0.2 part of リ are added, and in the same manner as in Production Example 1, the reaction is further continued until the conversion becomes 100%, and the Tg is −32.4 ° C. A solution of the copolymer (C15) was obtained.

[0105] Copolymer (C15) shows a continuous peak without a clear minimum value in GPC, a high molecular weight component (A3-15) having a molecular weight of 150,000 or more, and a molecular weight of 150,000. Containing less than low molecular weight components (B3-15)! The weight average molecular weight of the high molecular weight component (A3-15) is 450,000, the weight average molecular weight of the low molecular weight component (B3-15) is 30,000, and the area ratio of both is (A3-15) / (B3-15) = It was 75/25.

<Comparative Production Example 7> The same procedure as in Production Example 1 except that the monomer yarn was 76 parts n-butenorea tallylate, 22 parts methinomethacrylate, 1.5 parts attalinoleic acid, 50 parts acetone, and 03 parts AIBNO. Then, the reaction was carried out until the conversion rate reached 75% to obtain a mixed solution of a copolymer and a monomer having a weight average molecular weight of 2.5 million.

Next, 200 parts of tonoleene, 0.5 parts of atalinoleic acid, 2 parts of タ are added, and the reaction is further carried out until the conversion becomes 100% in the same manner as in Production Example 1, and the Tg is -32.4 ° C. A solution of the copolymer (C 16) was obtained.

[0107] The copolymer (C16) does not contain a polymer having a molecular weight of less than 150,000, has a weight average molecular weight of 250,000, a Tg of 32. 1 ° C, a high molecular weight component (A1-16), It contained no more than 150,000 polymers and contained a low molecular weight component (B1-16) with a weight average molecular weight of 30,000 and a Tg of -33.2 ° C. The high molecular weight component (A1-16) and the low molecular weight component (B1-16) show two independent peaks in the GPC emission curve, and the area ratio between them is (Al-16) / (B1 — 16) = 75/25.

Manufacture example except that the monomer composition is 95 parts of n-butinorea tallylate and 5 parts of atalinoleic acid, and 100 parts of ethynole acetate and 0.2 parts of benzoyl peroxide instead of 100 parts of acetone and 03 parts of AIBNO. In the same manner as in 6, the reaction was allowed to proceed for 10 hours until the conversion reached 100%, and the Tg was 49.3 ° C, the weight average molecular weight was 1,500,000, and the high molecular weight copolymer (A1 — A solution of 17) was obtained. The resulting copolymer solution was diluted with ethyl acetate to adjust the nonvolatile concentration to 20%.

[0109] Separately, the monomer composition was 65 parts of n-butenorea talelate, 30 parts of methenoremethalate, 5 parts of atharinoleamide, and instead of 150 parts of toluene and 03 parts of AIBNO. Except for using 2 parts of AIBN and 2 parts of n-lauryl mercaptan, the reaction was conducted for 6 hours until the conversion reached 100% in the same manner as in Production Example 6, Tg was -17.2 ° C, and the weight average molecular weight was 10,000. A solution of a low molecular weight copolymer (B1-17) containing no component having a molecular weight of 150,000 or more was obtained. The obtained copolymer solution was diluted with toluene to adjust the nonvolatile content concentration to 40%.

[0110] Next, the weight specific force between the high molecular weight copolymer (A1-17) and the low molecular weight copolymer (B1-17) (A1-17) / (B1-17) = 100/150 , Mix both copolymer solutions, A copolymer (C17) solution having a Tg of −31 · 1 ° C. was obtained.

Copolymer (C17) does not contain a polymer with a molecular weight of less than 150,000, has a weight average molecular weight of 150,000, a Tg of 49.3 ° C, a high molecular weight component (A1-17), and a molecular weight of 150,000 or more. And a low molecular weight component (B1-17) having a weight average molecular weight of 10,000 and a Tg of −17.2 ° C. The high molecular weight component (A1-17) and the low molecular weight component (B1-17) show two independent peaks in the GPC emission curve, and the area ratio between them is (Al-17) / (B1 — 17) = 75/25.

The alkyl methacrylate (a) had no substituents constituting the copolymer (C17) and was about 18%.

[0111] <Comparative Production Example 9>

The monomer composition is 95 parts of η-butinorea tallylate and 5 parts of attalinoleic acid. Instead of 100 parts of acetone and 0.03 parts of acetone, 0.3 part of benzoyl peroxide, 40 parts of ethyl acetate, 60 parts of toluene In the same manner as in Production Example 6, except that the reaction was carried out for 10 hours until the conversion rate reached 100%, and it contained components with a Tg of -49.3 ° C, a weight average molecular weight of 1 million, and a molecular weight of less than 15. A high molecular weight copolymer (A1-18) solution was obtained. The obtained copolymer solution was diluted with ethyl acetate to adjust the nonvolatile content concentration to 20%.

[0112] Separately, the monomer composition was 99 parts methyl metatalylate and 1 part acrylic acid, but instead of 150 parts toluene and AIBN 0.03 parts, AIBN 1 part, ethyl acetate 40 parts, toluene 60 parts In the same manner as in Production Example 6, the reaction was allowed to proceed for 6 hours until the conversion reached 100%, and the Tg was 105 ° C, the weight average molecular weight was 20,000, and the low molecular weight A polymer (B1-18) solution (nonvolatile content: 50%) was obtained.

[0113] Next, the weight specific force between the high molecular weight copolymer (A1-18) and the low molecular weight copolymer (B1-18) is (A1-18) / (B1-18) = 48/52 Both copolymer solutions were mixed to obtain a copolymer (C18) solution having a Tg of 10.5 ° C. When GPC was measured for copolymer (C18), it had two independent peaks, and the area と between high molecular weight copolymer (A1-18) and low molecular weight copolymer (B1-18) was ( A1-18) / (B1-18) = 48/52.

The alkyl methacrylate (a) had no substituents constituting the copolymer (C18) and was about 51.5%. [0114] <Comparative Production Example 10>

Manufactured except that the monomer composition is 98 parts of n-butyl acrylate, 1 part of acrylic acid, 1 part of acrylamide, and 100 parts of ethyl acetate and 0.03 parts of AIBN instead of 100 parts of acetone and AIBNO. 03 parts. In the same manner as in Example 6, the reaction is allowed to proceed for 8 hours until the conversion reaches 100%. Thus, a high molecular weight copolymer (A3-19) solution was obtained. The resulting copolymer solution was diluted with ethyl acetate to adjust the nonvolatile content concentration to 25%.

[0115] Separately, the monomer composition is 86.4 parts of n-butinorea tallylate and 13.6 parts of methinoremethalate, and instead of 150 parts of toluene and 0.03 parts of AIBN, 200 parts of ethyl acetate, Except for AIBN of 0.03 part, the reaction was conducted for 4 hours until the conversion rate reached 100% in the same manner as in Production Example 6, the Tg was -40.7 ° C, the weight average molecular weight was 300,000, and the molecular weight A high molecular weight copolymer (A3-19 ′) solution containing more than 100,000 components was obtained. The obtained copolymer solution was diluted with ethyl acetate to adjust the nonvolatile content concentration to 25%.

Next, both copolymer solutions were prepared so that the weight specific force between the high molecular weight copolymers (A3-19) and (A3-19 ') was (A3-19) / (A3-19') = 100/30. By mixing, a copolymer (C 19) solution having a Tg of −49 · 7 ° C. was obtained. Without the substituent constituting the copolymer (C19)! /, The alkylmetatalate (a) was about 3.1%.

The copolymer (C19) shows a continuous peak without a clear minimum value in GPC, and the area ratio between the high molecular weight side and the low molecular weight side with a molecular weight of 150,000 is 83/17. The weight average molecular weight on both sides of the high molecular weight was 550,000, and the weight average molecular weight on the low molecular weight side was 80,000.

[0116] <Comparative Production Example 11>

Manufacture example 6 except that the monomer composition was 95 parts of n-butinorea tallylate and 5 parts of atalinoleic acid, and instead of 100 parts of acetone and 0.03 parts of AIBN, 100 parts of ethyl acetate and 0.2 parts of AIBN were used. In the same way as above, the reaction is allowed to proceed for 12 hours until the conversion reaches 100%, the Tg is 49.3 ° C, the weight average molecular weight is 1.5 million, and the high molecular weight copolymer containing no component with a molecular weight of less than 150,000 is contained. A polymer (A1-20) solution was obtained. The resulting copolymer solution was diluted with ethyl acetate to adjust the nonvolatile content concentration to 20%. [0117] Separately, the monomer composition was changed to 100 parts of n-butinorea tallylate, and instead of 150 parts of toluene and 03 parts of AIB NO. 03 parts of toluene, 5 parts of α-methylstyrene dimer as a chain transfer agent, In the same manner as in Production Example 6 except that 2 parts were used, the reaction was allowed to proceed for 6 hours until the conversion reached 100%, the Tg was -54 ° C, the weight average molecular weight was 7000, and the molecular weight was 150,000 or more. A low molecular weight copolymer (B1-20) solution containing no components was obtained. The resulting copolymer solution was diluted with toluene to adjust the nonvolatile content concentration to 40%.

[0118] Next, the weight ratio between the high molecular weight copolymer (A1-20) and the low molecular weight copolymer (B1-20) is such that both copolymers are (A19) / (B19) = 100/100 The solution was mixed to obtain a copolymer (C19) solution having a Tg of -5.1.7 ° C.

The copolymer (C120) had no substituent! /, And the alkyl methacrylate (a) was 0%. GPC of copolymer (C20) was measured and found to have two independent peaks. The area ratio of high molecular weight copolymer (A1-20) to low molecular weight copolymer (B1-20) is ( A1—20) / (B1—20) = 50/50.

[0119] The above production examples are summarized in Tables 1 to 3.

The abbreviations of monomers in Tables! To 3 are shown below.

ΒΑ: Butyl acrylate

2ΕΗΑ: 2-Ethylhexyl acrylate

ΜΜΑ: Methyl metatalylate

ΒΜΑ: Butylmetatalylate

ΑΑ: Acrylic acid

ΜΑΑ: Methacrylic acid

2ΗΕΜΑ: 2-hydroxyethyl methacrylate

4ΗΒΑ: 4-Hydroxybutyl acrylate

4EG—Α: Light Atylate 4EG— A (PEG # 200 Diatalylate, manufactured by Kyoeisha Chemical Co., Ltd.)

AAm: Acrylamide

[0120] [Table 1] Table 1 (Production example)

* "Molecular weight range classification": Minimum value or 150,000

Table 2 (Comparative production example)

* "Molecular weight range classification": Minimum value or 150,000

3 »瞓 ^" 困困 s «_ <* :.

The weight average molecular weight of the copolymer is the polystyrene-reduced weight average molecular weight determined by GPC measurement, and the GPC measurement conditions are as follows.

Equipment: Shodex GPC System-21 (made by Showa Denko KK)

Column: A total of 3 Shodex KF-602. 5 and 2 Shodex KF-606M (Akira Higuchi Electric Works Co., Ltd.) are connected and used.

Solvent: Tetrahydrofuran

Flow rate: 0, 5ml / min

Temperature: 40 ° C Sample concentration: 0. lwt%

Sample injection volume: 50 1

[0124] <Example 1>

To 100 parts of the solid content of the copolymer (C1) solution obtained in Production Example 1, an isocyanate curing agent (trimethylolpropane adduct of tolylene diisocyanate; the same shall apply hereinafter) is used as an active ingredient. Add 2 parts of Silane Coupling Agent 1 (3-glycidoxypropyltrimethoxysilane; the same shall apply hereinafter) as the active ingredient and stir well to give the adhesive composition (pressure-sensitive adhesive composition). Obtained. The obtained adhesive composition was subjected to various tests as described later.

Adhesive composition in the same manner as in Example 1 except that each of the copolymer (C2) to (C3) solutions obtained in Production Examples 2 to 3 was used instead of the copolymer (C1) solution. And evaluated in the same manner as in Example 1.

Instead of the copolymer (C1) solution, using the copolymer (C4) solution obtained in Production Example 4, 0.15 parts of the isocyanate curing agent as an active ingredient and the epoxy curing agent 1 (N, N, Ν ', Ν' -tetraglycidyl-m-xylenediamine (the same applies hereinafter) were used in the same manner as in Example 1 except that 0 · 05 parts were used as active ingredients. Evaluation was performed in the same manner as in Example 1.

Adhesive composition as in Example 1, except that the copolymer (C5) to (C9) solutions obtained in Production Examples 5 to 9 were used instead of the copolymer (C1) solution, respectively. And evaluated in the same manner as in Example 1.

[0128] <Comparative Example 1>

With respect to 100 parts of the solid content of the copolymer (C10) solution obtained in Comparative Production Example 1, 0.05 part of the isocyanate curing agent is used as the active ingredient, and 0.5 part of the silane coupling agent 1 is used as the active ingredient. 1 part was added and stirred well to obtain an adhesive composition. When evaluated in the same manner as in Example 1, foaming occurred in the heat resistance test and the moist heat resistance test.

[0129] <Comparative Examples 2 to 7> Adhesive composition in the same manner as in Example 1 except that each of the copolymers (C11) to (C16) solutions obtained in Comparative Production Examples 2 to 7 was used instead of the copolymer (CI) solution. The product was obtained and evaluated in the same manner as in Example 1.

[0130] <Comparative Example 8>

To the solid content of 250 parts of the copolymer (C17) solution obtained in Comparative Production Example 8, 0.02 part of epoxy curing agent 1 as an active ingredient was added and stirred well to obtain an adhesive composition.

The obtained adhesive composition was evaluated in the same manner as in Example 1. As a result, the substrate adhesion was remarkably poor, and remarkable foaming was observed in the heat resistance test and the moist heat resistance test.

[0131] <Comparative Example 9>

Add 100 parts of epoxy hardener 2 (ethylene glycol diglycidyl ether; the same shall apply hereinafter) as an active ingredient to 100 parts of the solid content of the copolymer (C18) solution obtained in Comparative Production Example 9. And stirred well to obtain an adhesive composition.

The obtained adhesive composition was evaluated in the same manner as in Example 1. As a result, a light leakage phenomenon in which the substrate adhesion and reworkability were remarkably deteriorated, and remarkable foaming was observed in the heat resistance test and the moist heat resistance test. It was.

[0132] <Comparative Example 10>

Add 0.6 part of Epoxy Curing Agent 1 as an active ingredient to 130 parts of the solid content of the copolymer (C19) solution obtained in Comparative Production Example 10 and stir well to obtain the adhesive composition. Obtained.

As a result of evaluating the obtained pressure-sensitive adhesive composition in the same manner as in Example 1, the substrate adhesion and reworkability were extremely bad.

[0133] <Comparative Example 11>

For 200 parts of the solid content of the copolymer (C20) solution obtained in Comparative Production Example 11, an ethylenic hardener (trimethylolpropane tree β-aziridinylpropionate) was added as an effective component. 2.5 parts of phenolic compound (3,5 tert-butyl-4-hydroxy monobenzylphosphonate-jetyl ester) as an active ingredient as an antioxidant, and silane coupling agent 2 (3 aminopropyl) 1 part of trimethoxysilane) was added as an active ingredient and stirred well to obtain an adhesive composition.

As a result of evaluating the obtained adhesive composition in the same manner as in Example 1, the adhesion to the substrate and the reworkability In the heat resistance test and wet heat resistance test, foaming was observed.

A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that the epoxy-based curing agent 1 was used instead of the isocyanate curing agent, and evaluated in the same manner as in Example 1. As a result of evaluation, the substrate adhesion was remarkably poor.

[0135] Various tests were performed as follows.

The adhesive composition obtained in each Example and each Comparative Example was applied to a polyester release film (thickness 38 m) and dried at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of 25 m. . A polarizing film (thickness 180 m) was bonded to the obtained adhesive layer, and the reaction was allowed to proceed for 7 days in an atmosphere of 23 ° C. and 50% RH (aging) to obtain an adhesive film 1.

The resulting adhesive film 1 was cut to a width of 25 mm, the release film was peeled off, and the exposed adhesive layer was attached to a 0.7 mm thick glass plate in a 23 ° C, 50% RH atmosphere, and a 50 ° C atmosphere. Then, after applying pressure of 5 kg / cm ² and holding for 15 minutes, bonding was performed in accordance with JIS Z 0237.

[0136] After 24 hours of pressure bonding, the mixture was allowed to stand at 80 ° C for 500 hours. Then, peel off the polarizing film from the glass plate at 23 ° C, 50% RH atmosphere using a peel tester at 180 ° peel and a pulling speed of 300 mm / min, and visually observe the glass plate surface and adhesive layer surface did. The evaluation criteria are as follows.

4: The pressure-sensitive adhesive layer has not been transferred to the glass plate surface at all, and the pressure-sensitive adhesive layer surface is also smooth.

3: The pressure-sensitive adhesive layer has not transferred to the glass plate surface, but slight unevenness is generated on the surface of the pressure-sensitive adhesive layer.

2: A part of the adhesive layer was transferred to the glass plate surface, and the surface of the adhesive layer was significantly uneven.

1: The adhesive layer has completely transferred to the glass plate surface.

[0137] <Light leakage phenomenon>

The adhesive composition obtained in each example and each comparative example was applied to a polyester release film (thickness 38 am) and dried at 90 ° C for 60 seconds to form an adhesive layer with a thickness of 25 and im did. A polarizing film (thickness 180 m) was bonded to the obtained adhesive layer, and the reaction was allowed to proceed for 7 days in an atmosphere of 23 ° C. and 50% RH (aging). Adhesive film 2 was obtained by cutting into 200 mm × 200 mm so that the axial direction force of the absorption axis of the polarizing film was at an angle of 45 ° to the side.

Peel off the release film of adhesive film 2 and place the exposed adhesive layer on both sides of a 0.7 mm thick glass plate so that the axis directions of the absorption axes of the polarizing films are perpendicular to each other. Apply 5 kg / cm ² under pressure, hold it for 15 minutes, bond it, leave it in an atmosphere of 80 ° C for 500 hours, return it to room temperature, and check for light leakage from the corners or peripheral edges Was observed. The evaluation criteria are as follows.

4: No light leakage is observed!

3: Les with almost no light leakage.

2: Light leakage is slightly noticeable.

1: Light leakage is extremely remarkable.

[0138] <Heat resistance and moist heat resistance>

Peel off the adhesive film 2 release film described in the light leakage phenomenon, and apply a pressure of 5 kg / cm ² under a 50 ° C atmosphere to one side of a 0.7 mm thick glass sheet. After holding for 5 minutes and bonding, it was left in an atmosphere at 80 ° C for 500 hours (heat resistance test). Separately, after the adhesive film 2 and the glass plate were bonded in the same manner, they were left in a constant temperature and humidity chamber at 60 ° C. and 90% RH for 500 hours (moisture and heat resistance test).

After standing, it was returned to room temperature, and the adhesive film 2 was observed to float and peel off and foamed.

Yes

[0139] "Foaming" is a state in which relatively large bubbles are generated at the interface between the adhesive layer and the glass (other than the peripheral edge).

“Floating / peeling” is a state in which the adhesive film 2 is lifted off the glass and peeled off. Each evaluation standard is as follows.

4: Not generated.

3: Minor occurrence is observed.

2: Occurrence is observed. 1: Significant occurrence is observed. The above evaluation results are shown in Tables 4-6.

[Table 4]

^ s Table 5

The abbreviations in 4-6 are as follows.

Isocyanate curing agent: Trimethylolpropane adduct of tolylene diisocyanate Epoxy curing agent 1: N, N, Ν ', Ν'-tetraglycidinole m-xylene diamine Epoxy curing agent 2: Ethylene glycol di Glycidyl ether Ethyleneimine curing agent: trimethylol propane tree β aziridinyl propionate

Antioxidants: 3,5-di-tert-butyl 4-hydroxy-benzylphosphonate ethinoleestenole

Silane coupling agent 1: 3-glycidoxypropyltrimethoxysilane

Silane coupling agent 2: 3 Aminopropyltrimethoxysilane

The disclosure of the present application is related to the subject matter described in Japanese Patent Application No. 2006-243715 filed on Sep. 8, 2006, the entire disclosure of which is incorporated herein by reference.

It should be noted that various modifications and changes may be made to the above-described embodiments without departing from the novel and advantageous features of the present invention other than those already described. Accordingly, all such modifications and changes are intended to be included within the scope of the appended claims.

Claims

Claims [1] A pressure-sensitive adhesive containing a copolymer (C) having a hydroxyl group and / or a carboxyl group and having a glass transition temperature of −60 to 0 ° C. and an isocyanate curing agent (D) Wherein the copolymer (C) is

A pressure-sensitive adhesive.

[2] The alkyl group of the unsubstituted alkyl methacrylate Ha) has 1 to 6 carbon atoms, and the alkyl group is a linear alkyl group, a chain alkyl group having a branched structure, and cyclic The pressure-sensitive adhesive according to claim 1, wherein the pressure-sensitive adhesive is at least one selected from the group consisting of alkyl groups.

[3] The pressure-sensitive adhesive according to claim 1 or 2, comprising 0.01 to 10 parts by weight of the isocyanate curing agent (D) with respect to 100 parts by weight of the copolymer (C).

[4] The copolymer (C) has an alkyl metatalylate (a) having no substituent: 15 to 35% by weight, has no substituent !, the alkyl acrylate (b) and the ω (b ) And other monomers having an ethylenically unsaturated double bond (C) having a hydroxyl group and / or a carboxy group and an ethylenically unsaturated double bond ( a copolymer containing a high molecular weight component having a weight average molecular weight of 500,000 to 200,000 by radical copolymerization of the monomer (c) containing c 1) until the polymerization conversion reaches 60 to 90%. Then, monomer (c) is added as necessary, and the above-mentioned (a) to (c) are further radically copolymerized until the polymerization conversion becomes 80 to 100%. The pressure-sensitive adhesive according to any one of claims 1 to 3, wherein

[5] A method for producing a pressure-sensitive adhesive comprising the following (I) to (III):

(I) Alkyl metatalylate having no substituent (a): 15 to 35% by weight, V having no substituent, alkyl attalate (b), and other copolymerizable with the above (a) and (b) A monomer (c) having an ethylenically unsaturated double bond and comprising a monomer (cl) having a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated double bond ( c) is radically copolymerized until the polymerization conversion force becomes 0 to 90% to obtain a copolymer containing a high molecular weight component having a weight average molecular weight of 500,000 to 2,200,000;

(2-2) Both sides of the minimum value of the discharge curve in gel permeation chromatography A high molecular weight component (A2) peak having a weight average molecular weight of 500,000 to 2,200,000 and a low molecular weight component (B2) peak having a weight average molecular weight of 1,000 to 100,000; The area ratio of the peak of the component (A2) and the peak of the low molecular weight component (B2) is (A2) / (B2) = 60/40 to 90/10, or

(III) Mixing the copolymer (C) with the isocyanate curing agent (D).

[6] A pressure-sensitive adhesive obtained by the production method according to claim 5.

[7] An optical film selected from the group consisting of a polarizing film and a retardation film, and a pressure-sensitive adhesive layer provided on at least one surface of the optical film, comprising: A pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive according to any one of the above.