TWI744354B - Rubber adhesive composition, rubber adhesive layer, adhesive film, optical film with rubber adhesive layer, optical component and image display device - Google Patents

Abstract

The present invention is a rubber-based adhesive composition comprising a rubber-based matrix polymer. The rubber-based matrix polymer contains an isobutylene-based polymer with a polydispersity (weight average molecular weight/number average molecular weight) of 4 or less, and is adhered by the rubber The 50μm thick rubber adhesive layer formed by the composition has a moisture permeability of 50g/(m ² .day) or less at 40°C and 92%RH. With the rubber-based adhesive composition of the present invention, a highly durable rubber-based adhesive layer can be formed with low moisture permeability, and can also inhibit the occurrence of defects such as floating or peeling in a high-temperature environment.

Description

Rubber adhesive composition, rubber adhesive layer, adhesive film, optical film with rubber adhesive layer, optical component and image display device

The present invention relates to a rubber-based adhesive composition and a rubber-based adhesive layer formed by the rubber-based adhesive composition. In addition, the present invention relates to an optical film with a rubber-based adhesive layer provided with the aforementioned rubber-based adhesive layer on the optical film, and an optical member with the aforementioned rubber-based adhesive layer provided on a low moisture permeability film. In addition, the present invention relates to an adhesive film containing the aforementioned rubber-based adhesive layer. In addition, the present invention relates to an image display device including the aforementioned adhesive layer-attached optical film and/or optical member.

In recent years, there has been a strong demand for weight reduction and thinning of image display devices such as liquid crystal display devices, and various optical components such as polarizing films used in image display devices are also expected to be thinner and lighter.

For example, the well-known polarizing film is a single-sided protective polarizing film having a protective film on only one side of the polarizer. Although such a single-sided protective polarizing film can be thinner and lighter in weight, since the single side of the polarizer is not protected by the protective film, there is a problem that it is prone to deterioration due to moisture and the like. In addition, even if it is a double-sided protective polarizing film, when the protective film is made into a thin film, the polarizer may be similarly degraded by moisture or the like.

In addition, the organic EL panel mounted in the organic EL (Electro Luminescence) display device is very intolerant to moisture or oxygen in the atmosphere. A barrier layer or an optical film with barrier function is often provided on the surface of the organic EL panel, and the adhesive layer used to bond these is also required to not allow moisture to pass through (low moisture permeability).

In this way, various optical components used in image display devices are easily degraded by moisture due to differences in their materials, and the adhesive layer used to bond the optical components to the adherend is required to be unable to transmit moisture, etc. (low moisture permeability) ).

The material for forming such a low moisture permeability adhesive layer is known as a rubber adhesive. For example, an adhesive encapsulating composition containing a hydrogenated cyclic olefin polymer and a polyisobutylene resin with a weight average molecular weight of 500,000 or more is known ( For example, refer to Patent Document 1), an adhesive composition containing a polyisobutylene resin with a weight average molecular weight of 270,000 to 480,000, a polyisobutylene resin with a weight average molecular weight of 100,000 to 250,000, and a hydrogenated petroleum resin with a softening point of 90 to 135°C (See, for example, Patent Document 2).

Prior art literature Patent literature

Patent Document 1: Japanese Patent Publication No. 2009-524705

Patent Document 2: Japanese Patent No. 5416316

Summary of the invention

Although the adhesive layer can be lowered when using rubber adhesives, it is better in high temperature environments than acrylic adhesives used in the past for optical applications. Under peeling or foaming deterioration. Such defects such as peeling or foaming are caused by insufficient cohesive force near the bonding interface of the rubber-based adhesive layer. It is known that the insufficient cohesive force near the adhesive interface is due to the fact that the rubber-based adhesive contained in the rubber-based adhesive has a small molecular weight and less entangled rubber-based polymer that exists in large quantities near the interface of the adhesive layer, resulting in a layer with low cohesive force ( Fragile layer).

Although Patent Documents 1 and 2 try to improve various problems by adding additives such as tackifiers to rubber-based polymers, the fundamental cause of the improvement of the rubber-based polymer itself has not been implemented. From the viewpoint of durability, it is not yet possible. full.

Therefore, the object of the present invention is to provide a rubber-based adhesive composition that can form a highly durable rubber-based adhesive layer that can form a low moisture permeability and can also prevent problems such as floating or peeling in a high-temperature environment. . Furthermore, the object of the present invention is to provide a rubber-based adhesive layer formed from the adhesive composition, an adhesive film provided with the rubber-based adhesive layer, an optical film with a rubber-based adhesive layer, and an optical member. In addition, the object of the present invention is also to provide an image display device including the aforementioned optical film and/or optical member with a rubber-based adhesive layer.

The inventors of the present invention intensively studied to solve the aforementioned problems, and as a result, found the following rubber-based adhesive composition and completed the present invention.

In other words, the present invention is a rubber-based adhesive composition containing a rubber-based matrix polymer. The rubber-based adhesive composition is characterized in that the rubber-based matrix polymer contains polydispersity (weight average molecular weight/number average molecular weight) 4 or less isobutylene-based polymer; the 50μm-thick rubber-based adhesive layer formed from the aforementioned rubber-based adhesive composition has a moisture permeability of 50g/(m ² .day) or less at 40°C and 92%RH.

The aforementioned rubber-based adhesive composition preferably contains a tackifier.

The aforementioned tackifier is preferably at least one tackifier selected from the group consisting of a tackifier containing a terpene skeleton, a tackifier containing a rosin skeleton, and these hydrides.

The softening point of the aforementioned tackifier is preferably above 90°C.

The aforementioned rubber-based adhesive composition preferably contains a hydrogen abstraction type photopolymerization initiator.

The present invention relates to a rubber-based adhesive layer formed from the aforementioned rubber-based adhesive composition.

The present invention relates to an adhesive film having a support body composed of a plastic substrate and the aforementioned rubber-based adhesive layer on at least one side of the support body.

The present invention relates to an optical film with a rubber-based adhesive layer, which has an optical film and the aforementioned rubber-based adhesive layer on at least one side of the optical film.

The aforementioned optical film is preferably a polarizing film having a protective film on at least one side of the polarizer.

The aforementioned polarizing film is a single-sided protective polarizing film having a protective film on only one side of the polarizer, and the aforementioned rubber-based film is sequentially laminated Adhesive layer, polarizer, and protective film are preferred. Furthermore, the optical film with the rubber-based adhesive layer may include a retardation film, and the rubber-based adhesive layer, the retardation film, the polarizer, and the protective film are preferably laminated in this order.

In addition, the present invention relates to an optical member having ^{a film having a moisture permeability of 1 g/(m 2} .day) or less at 40° C. and 92% RH, and the aforementioned rubber-based adhesive layer on at least one side of the film .

In addition, the present invention relates to an image display device characterized by comprising at least one optical film with a rubber-based adhesive layer or the optical member.

The rubber-based adhesive composition of the present invention uses a low-molecular-weight rubber-based polymer, that is, a polymer with a small polydispersity (Mw/Mn). It can suppress the (highly durable) rubber-based adhesive layer caused by defects (floating or peeling, etc.).

In addition, the present invention can provide a rubber-based adhesive layer-attached optical film or optical member with excellent durability and low moisture permeability in a high-temperature environment, an adhesive film, and an image display device with excellent optical reliability.

1: Polarizing film with adhesive layer

2: Polarizing film

3: Rubber adhesive layer

4: Polarizing parts

5: Protective film

6: retardation film

Fig. 1 is a schematic cross-sectional view of a polarizing film with an adhesive layer according to an embodiment of the present invention.

Fig. 2 is a cross-sectional view schematically showing a polarizing film with an adhesive layer according to an embodiment of the present invention.

The form used to implement the invention

1. Rubber adhesive composition

The rubber-based adhesive composition of the present invention includes a rubber-based matrix polymer; the aforementioned rubber-based matrix polymer includes an isobutylene-based polymer with a polydispersity (weight average molecular weight/number average molecular weight) of 4 or less; composed of the aforementioned rubber-based adhesive The moisture permeability of the rubber-based adhesive layer with a thickness of 50μm at 40°C and 92%RH is below 50g/(m ² .day).

(1) Rubber-based matrix polymer

The rubber-based matrix polymer used in the present invention is a polymer that exhibits rubber elasticity in a temperature range around room temperature, and includes an isobutylene-based polymer with a polydispersity (weight average molecular weight/number average molecular weight) of 4 or less.

Examples of the aforementioned isobutylene-based polymer include those containing isobutylene as a constituent monomer. The aforementioned isobutylene-based polymer can be a homopolymer of isobutylene (polyisobutylene, PIB), or a copolymer with isobutylene as the main monomer (ie, a copolymer copolymerized with isobutylene at a ratio of greater than 50 mol%) ). Such copolymers include, for example, copolymers of isobutylene and n-butene, copolymers of isobutylene and isoprene (such as regular butyl rubber, chlorinated butyl rubber, bromobutyl rubber, partially cross-linked butyl Butyl rubbers such as rubber), these vulcanized products or modified products (for example, those modified with functional groups such as hydroxyl, carboxyl, amine, and epoxy), etc. In view of the fact that the main chain does not contain a double bond and is excellent in weather resistance, polyisobutylene (PIB) is also preferred among these.

The polydispersity of the isobutylene polymer can be calculated from the ratio (Mw/Mn) of the weight average molecular weight (Mw) of the isobutylene polymer to the number average molecular weight (Mn). In the present invention, the polydispersity of isobutylene polymer (Mw/Mn) is 4 or less, preferably 3.5 or less, and more preferably 3 or less. The lower limit of the polydispersity is not particularly limited, but 1 or more is preferred. In the present invention, if the polydispersity of the isobutylene-based polymer is 4 or less, the durability of the rubber-based adhesive layer obtained from the rubber-based adhesive composition will be good. This is because by using an isobutylene-based polymer with a polydispersity of 4 or less, the low-molecular-weight component in the rubber-based adhesive composition will be reduced, and the rubber-based adhesive layer formed by the adhesive composition can be suppressed It is formed by a fragile layer formed by low molecular weight components.

The aforementioned isobutylene-based polymer with a polydispersity of 4 or less can be used, for example, OPPANOL N series manufactured by BASF Corporation and other commercially available products. Specifically, OPPANOL N50 (Mw/Mn: 2.3) manufactured by BASF Corporation, OPPANOL N80 may be used. (Mw/Mn: 2.4), OPPANOL N100 (Mw/Mn: 2.9), etc. as examples.

The weight average molecular weight (Mw) of the aforementioned isobutylene-based polymer is preferably 500,000 or more, preferably 550,000 or more, preferably 700,000 or more, and more preferably 1 million or more. In addition, the upper limit of the weight average molecular weight is not particularly limited, but is preferably 5 million or less, more preferably 3 million or less, and more preferably 2 million or less. Since the weight average molecular weight of the isobutylene-based polymer is set to 500,000 or more, it tends to be an adhesive composition with better durability when stored at high temperatures, so it is preferable.

The number average molecular weight (Mn) of the aforementioned isobutylene-based polymer is preferably 200,000 or more, more preferably 300,000 or more, and more preferably 400,000 or more. In addition, the upper limit of the number average molecular weight is not particularly limited, but is preferably 3 million or less, preferably 1 million or less, and more preferably 700,000 or less. due to By setting the number-average molecular weight of the isobutylene-based polymer to 200,000 or more, the cohesive force of the polymer is increased, and defects such as peeling during high-temperature storage can be suppressed, which is preferable.

[ That is, it is particularly preferable that the rubber-based matrix polymer is composed of only an isobutylene-based polymer having a polydispersity of 4 or less. In addition, the upper limit is not particularly limited, as long as it is, for example, 100% by weight or less.

In addition, the rubber-based adhesive composition of the present invention may include a rubber-based polymer other than the aforementioned isobutylene-based polymer. Specifically, for example, styrene-ethylene-butene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene -Styrenic block copolymer (SBS), styrene-ethylene-propylene-styrene block copolymer (SEPS, SIS hydrogenated product), styrene-ethylene-propylene block copolymer (SEP, styrene-iso Hydrogenated product of pentadiene block copolymer), styrene-isobutylene-styrene block copolymer (SIBS), styrene-butadiene rubber (SBR) and other styrene-based block copolymers, etc. Plastic elastomer; butyl rubber (IIR), butadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), EPR (binary ethylene-propylene rubber), EPT (ternary ethylene-propylene rubber) ), acrylic rubber, urethane rubber, polyurethane-based thermoplastic elastomer; polyester-based thermoplastic elastomer; blending of polypropylene and EPT (ternary ethylene-propylene rubber) polymer Blends such as materials are thermoplastic elastomers and the like. Can not impair the effect of the present invention These are added within the range, but the aforementioned rubber-based matrix polymer is preferably 40% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, or not included (that is, 0% by weight).

The content of the aforementioned rubber-based matrix polymer is not particularly limited. In the total solid content of the rubber-based adhesive composition, it is preferably 40% by weight or more, preferably 50% by weight or more, and more preferably 70% by weight or more. More than 80% by weight is particularly preferred. The upper limit of the content of the rubber-based matrix polymer is not particularly limited, but is preferably 100% by weight or less, and more preferably 90% by weight or less.

The moisture permeability of the rubber-based adhesive layer with a thickness of 50μm formed from the aforementioned rubber-based adhesive composition is 50g/(m ² .day) or less, preferably 30g/(m ² .day) or less, and 20g/(m) ^2. Day) or less is preferable, and 15g/(m ² .day) or less is more preferable. In addition, the lower limit of the moisture permeability is not particularly limited, and ideally, it is preferable that no water vapor is permeated at all (that is, 0 g/(m ² .day)). As long as the moisture permeability of the rubber-based adhesive layer is within the aforementioned range, when the adhesive layer is used in an optical film such as a polarizing film, the migration of moisture to the optical film can be suppressed, and the deterioration of the optical film caused by moisture can be suppressed, so it is preferable . The water vapor transmission rate (water vapor transmission rate) of the rubber adhesive layer with a thickness of 50 μm under the conditions of 40° C. and 92% RH can be measured by the method described in the examples.

(2) Tackifier

A tackifier can be added to the rubber-based adhesive composition of the present invention. The tackifier may include at least one tackifier selected from the group consisting of a tackifier containing a terpene skeleton, a tackifier containing a rosin skeleton, and these hydrides. By including the tackifier in the rubber-based adhesive composition, it can form Pairs of various adherends have a rubber-based adhesive layer that has high adhesion and high durability under high temperature environments, so it is preferred.

The aforementioned tackifier containing a terpene skeleton may include terpene polymers such as α-pinene polymer, β-pinene polymer, and dipentene polymer, or after modification (phenol modification, styrene modification, etc.) , Aromatic modification, hydrogenation modification, hydrocarbon modification, etc.) The modified terpene resin after the aforementioned terpene polymer is taken as an example. Examples of the aforementioned modified terpene resin include terpene phenol resin, styrene modified terpene resin, aromatic modified terpene resin, hydrogenated terpene resin (hydrogenated terpene resin), and the like. Examples of the hydrogenated terpene resin referred to here include hydrogenated terpene polymers, other modified terpene resins, and hydrogenated terpene phenol resins. From the viewpoint of compatibility with rubber-based adhesive compositions or adhesive properties, among these, hydrogenated terpene phenol resins are also preferred.

The aforementioned tackifiers containing rosin skeletons include rosin resins, polymerized rosin resins, hydrogenated rosin resins, rosin ester resins, hydrogenated rosin ester resins, and rosin phenol resins as examples. Specifically, rosin gum, wood rosin, Unmodified rosin (raw rosin), such as pine oil rosin, or modified rosin after hydrogenation, heterogeneity, polymerization, or other chemical modification, or derivatives thereof.

As the aforementioned tackifier, for example, commercially available products such as Clearon series manufactured by Yasuhara Chemical Co., Ltd., Poly-star series, Super ester series manufactured by Arakawa Chemical Industry Co., Ltd., Pensel series, Pinecrystal series, etc. can be used.

When the aforementioned tackifier is a hydride, the hydrogenation may be a partially hydrogenated partial hydride, or all double bonds in the compound may be hydrogenated Fully hydride. In the present invention, from the standpoint of adhesive properties, weather resistance, or hue, a completely hydrogenated compound is preferred.

From the viewpoint of adhesive properties, the aforementioned tackifier preferably contains a cyclohexanol skeleton. The detailed principle is not yet clear, but it can be considered that the cyclohexanol skeleton is more compatible with the isobutylene-based polymer of the matrix polymer than the phenol skeleton. The tackifier containing a cyclohexanol skeleton is preferably, for example, hydrogenated products of terpene phenol resin and rosin phenol resin, and more preferably completely hydrogenated products of terpene phenol resin and rosin phenol resin.

The softening point (softening temperature) of the aforementioned tackifier is not particularly limited. For example, it is preferably about 90°C or higher, and preferably about 100°C or higher. This is because when the softening point of the tackifier is above 90°C, the tackifier does not soften and maintains its adhesive properties even at high temperatures, so it is preferred. The upper limit of the softening point of the tackifier is not particularly limited, but when the softening point is too high, the molecular weight will become higher, and there may be problems such as deterioration of compatibility and whitening, so for example, it is about 200°C or less Preferably, it is preferably below 180°C. In addition, the softening point of the tackifying resin referred to here is defined as a value measured in accordance with the softening point test method (Ring and Ball method) specified in either of JIS K5902 and JIS K2207.

The weight average molecular weight (Mw) of the aforementioned tackifier is not particularly limited, but is preferably 50,000 or less, preferably 30,000 or less, preferably 10,000 or less, more preferably 8,000 or less, and particularly preferably 5,000 or less. In addition, the lower limit of the weight average molecular weight of the aforementioned tackifier is not particularly limited, but it is preferably 500 or more, more preferably 1,000 or more, and more preferably 2,000 or more. If the weight average molecular weight of the aforementioned tackifier is within the aforementioned range, it is polymerized with isobutylene The compatibility of the material is good, and there will be no undesirable conditions such as whitening, so it is better.

With respect to 100 parts by weight of the solid content of the rubber-based matrix polymer, the amount of the tackifier added is preferably 40 parts by weight or less, preferably 30 parts by weight or less, and more preferably 20 parts by weight or less. In addition, the lower limit of the added amount of the tackifier is not particularly limited, but it is preferably 0.1 part by weight or more, preferably 1 part by weight or more, and more preferably 5 parts by weight or more. If the usage amount of the tackifier is within the aforementioned range, it is better because the adhesive properties can be improved. In addition, when the amount of the tackifier used is larger than the aforementioned range, the cohesive force of the tackifier tends to decrease, which is not preferable.

In addition, the rubber-based adhesive composition of the present invention may also contain tackifiers other than the tackifier containing the terpene skeleton and the tackifier containing the rosin skeleton. The tackifier can be a petroleum resin tackifier as an example. The aforementioned petroleum-based tackifiers can include, for example, aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins (aliphatic cyclic petroleum resins), and aliphatic petroleum resins. Aromatic petroleum resin, aliphatic. Alicyclic petroleum resin, hydrogenated petroleum resin, lavender ketone resin, lavender indene resin, etc.

The aforementioned petroleum resin-based tackifier can be used within a range that does not impair the effects of the present invention. For example, about 30 parts by weight or less can be used relative to 100 parts by weight of the solid content of the aforementioned rubber-based matrix polymer.

(3) Hydrogen abstraction type photopolymerization initiator

A hydrogen abstraction type photopolymerization initiator can be added to the rubber-based adhesive composition of the present invention. The hydrogen abstraction type photopolymerization initiator is irradiated with active energy rays so that the initiator itself does not crack, and it abstracts hydrogen from the isobutylene polymer such as polyisobutylene, and can form a reaction point in the polymer. By forming this reaction point, The cross-linking reaction of the polymer begins.

In addition to the hydrogen abstraction type photopolymerization initiator used in the present invention, the photopolymerization initiator is also known as a cleavage type photopolymerization initiator that cracks and decomposes the photopolymerization initiator itself by irradiating active energy rays to generate free radicals. However, when a cleavage-type photopolymerization initiator is used for the isobutylene-based polymer used in the present invention, the main chain of the isobutylene-based polymer will be cut by the photopolymerization initiator that has generated free radicals and cannot be crosslinked. In the present invention, by using a hydrogen abstraction type photopolymerization initiator, the crosslinking of the isobutylene-based polymer can be performed as described above.

、2,4-二甲基9-氧硫

、2,4-二乙基9-氧硫

、2,4-二氯9-氧硫

等9-氧硫

系化合物；4,4’-雙(二甲胺)二苯基酮、4,4’-二乙胺基二苯基酮等胺基二苯基酮系化合物；10-丁基-2-氯吖啶酮、2-乙基蒽醌、9,10-菲醌、樟腦醌等；萘乙酮、1-羥基環己基苯基酮等芳香族酮化合物；對苯二甲醛等芳香族醛、甲基蒽醌等醌系芳香族化合物。該等可單獨使用1種、或混合2種以上使用。由反應性之點來看，該等中亦以二苯基酮系化合物為佳，以二苯基酮較佳。 Hydrogen abstraction type photopolymerization initiators include, for example, acetophenone, diphenylketone, methyl phthalate, 4-phenyldiphenylketone, 4,4'-dichlorodiphenyl Ketone, hydroxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dimethylbenzophenone, 4-benzene Methyl-4'-methyl-diphenyl sulfide, acrylated diphenyl ketone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl) diphenyl ketone, 3, Diphenyl ketone compounds such as 3'-dimethyl-4-methoxybenzophenone; 2-isopropyl 9-oxysulfur

, 2,4-Dimethyl 9-oxysulfur

, 2,4-Diethyl 9-oxysulfur

, 2,4-Dichloro 9-oxysulfur

9-oxysulfur

Series compounds; 4,4'-bis(dimethylamine) diphenyl ketone, 4,4'-diethylamino diphenyl ketone and other amino diphenyl ketone series compounds; 10-butyl-2-chloro Acridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, etc.; aromatic ketone compounds such as naphthophenone and 1-hydroxycyclohexyl phenyl ketone; aromatic aldehydes such as terephthalaldehyde, methyl Quinone-based aromatic compounds such as anthraquinone. These can be used individually by 1 type or in mixture of 2 or more types. From the viewpoint of reactivity, among these, benzophenone-based compounds are preferred, and benzophenone is preferred.

With respect to 100 parts by weight of the aforementioned rubber-based matrix polymer, The content of the aforementioned hydrogen abstraction type photopolymerization initiator is preferably 0.001 to 10 parts by weight, preferably 0.005 to 10 parts by weight, and more preferably 0.01 to 10 parts by weight. By containing the hydrogen abstraction type photopolymerization initiator within the aforementioned range, the crosslinking reaction can be progressed to the desired density, which is preferable.

In the present invention, a cleavage-type photopolymerization initiator and the aforementioned hydrogen abstraction-type photopolymerization initiator may be used together within a range that does not impair the effects of the present invention, but it is preferable not to use them for the aforementioned reasons.

(4) Multifunctional radical polymerizable compound

The rubber-based adhesive composition of the present invention may further include a multifunctional radical polymerizable compound. In the present invention, the polyfunctional radical polymerizable compound functions as a crosslinking agent for the isobutylene-based polymer.

烷二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊 四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、EO改質二甘油四(甲基)丙烯酸酯等(甲基)丙烯酸與多元醇之酯化物、9,9-雙[4-(2-(甲基)丙烯醯氧基乙氧基)苯基]茀等。該等可單獨使用1種、或使用2種以上之混合物。該等中，由對異丁烯系聚合物之相溶性的觀點來看，以(甲基)丙烯酸與多元醇之酯化物為佳，以具2個(甲基)丙烯醯基之2官能(甲基)丙烯酸酯、具3個以上(甲基)丙烯醯基之3官能(甲基)丙烯酸酯較佳，以三環癸烷二甲醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯特佳。 The aforementioned polyfunctional radical polymerizable compound is a compound having at least two radical polymerizable functional groups having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group. Specific examples of the polyfunctional radical polymerizable compound include, for example, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylic acid Ester, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-ethyl-2-butylpropanediol bis(methyl) )Acrylate, bisphenol A di(meth)acrylate, bisphenol A ethylene oxide adduct di(meth)acrylate, bisphenol A propylene oxide adduct di(meth)acrylate, Bisphenol A propylene oxide ether di(meth)acrylate, neopentane glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, two

Alkyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate, two new Pentyleneerythritol penta(meth)acrylate, dineopentaerythritol hexa(meth)acrylate, EO modified diglycerol tetra(meth)acrylate, etc. (meth)acrylic acid and polyol esters, 9 , 9-Bis[4-(2-(meth)propenyloxyethoxy)phenyl]茀 and so on. These can be used individually by 1 type, or a mixture of 2 or more types can be used. Among them, from the viewpoint of compatibility with isobutylene-based polymers, the esterified product of (meth)acrylic acid and polyol is preferred, and the bifunctional (methyl) ) Acrylates, trifunctional (meth)acrylates with 3 or more (meth)acrylic acid groups are preferred, and tricyclodecane dimethanol di(meth)acrylate, trimethylolpropane tri(meth)acrylate Base) acrylate is particularly preferred.

The content of the polyfunctional radical polymerizable compound is preferably 20 parts by weight or less, preferably 15 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of the rubber-based matrix polymer. In addition, the lower limit of the content of the polyfunctional radical polymerizable compound is not particularly limited, but, for example, it is preferably 0.1 parts by weight or more, preferably 0.5 parts by weight or more, with respect to 100 parts by weight of the aforementioned rubber-based matrix polymer. More preferably 1 part by weight or more. If the content of the polyfunctional radical polymerizable compound is within the aforementioned range, it is preferable from the viewpoint of durability of the resulting rubber-based adhesive layer.

The molecular weight of the polyfunctional radical polymerizable compound is not particularly limited, but is preferably about 1,000 or less, and more preferably about 500 or less, for example.

(5) Other additives

An organic solvent may be added as a diluent to the aforementioned rubber-based adhesive composition. The diluent is not particularly limited, but toluene, xylene, n-heptane, dimethyl ether, etc. can be cited as examples. These can be used singly or as a mixture of two or more. use. Among these, toluene is also preferred.

The addition amount of the diluent is not particularly limited, and it is preferable to add about 50 to 95% by weight to the rubber-based adhesive composition, and more preferably about 70 to 90% by weight. If the addition amount of the diluent is within the aforementioned range, it is preferable from the viewpoint of the coatability to a support or the like.

In the rubber-based adhesive composition of the present invention, additives other than the foregoing may be added within a range that does not impair the effects of the present invention. Specific examples of additives include softeners, crosslinking agents (for example, polyisocyanates, epoxy compounds, alkyl etherified melamine compounds, etc.), fillers, anti-aging agents, ultraviolet absorbers, and the like. Depending on the purpose, the type, combination, addition amount, etc. of the additives added to the rubber-based adhesive composition can be appropriately set. The content (total amount) of the aforementioned additives in the rubber adhesive composition is preferably 30% by weight or less, preferably 20% by weight or less, and more preferably 10% by weight or less.

2. Rubber adhesive layer

The rubber-based adhesive layer of the present invention is characterized by being formed of the aforementioned rubber-based adhesive composition. The manufacturing method of the rubber-based adhesive layer of the present invention is described later.

The thickness of the rubber-based adhesive layer of the present invention is not particularly limited, and can be appropriately set depending on its use. However, it is preferably 250 μm or less, preferably 100 μm or less, and more preferably 50 μm or less. In addition, the lower limit of the thickness of the adhesive layer is not particularly limited, but from the viewpoint of durability, it is preferably 1 μm or more, and more preferably 5 μm or more.

The moisture permeability of the rubber-based adhesive layer of the present invention is as described above.

3. Manufacturing method of rubber adhesive layer

The manufacturing method of the rubber-based adhesive layer of the present invention is not particularly limited. For example, after coating the aforementioned rubber-based adhesive composition on various supports, etc., the rubber-based adhesive layer can be formed by removing the solvent by heating and drying. Manufacturing method 1). In addition, when the rubber-based adhesive composition of the present invention contains the hydrogen abstraction initiator, the rubber-based adhesive composition can be manufactured by irradiating the rubber-based adhesive composition with active energy rays to crosslink the isobutylene-based polymer. (Manufacturing method 2). Hereinafter, each manufacturing method will be described.

(1) Manufacturing method 1

Various methods can be used for the coating method of the adhesive composition. Specifically, for example: roll coating, touch roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating Methods such as cloth, curtain coating, lip die coating, extrusion coating using die coaters, etc.

The aforementioned heating and drying temperature is preferably about 30°C to 200°C, preferably 40°C to 180°C, and more preferably 80°C to 150°C. By setting the heating temperature within the aforementioned range, an adhesive layer with excellent adhesive properties can be obtained. The drying time can be appropriate and appropriate time. The aforementioned drying time is preferably about 5 seconds to 20 minutes, preferably 30 seconds to 10 minutes, and more preferably 1 minute to 8 minutes.

As the aforementioned support, for example, a sheet (separator) subjected to a peeling treatment can be used.

The constituent materials of the aforementioned separator include, for example, plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and non-woven fabrics, nets, foamed sheets, Metal foil, Appropriate sheets such as these laminates, etc., but from the viewpoint of excellent surface smoothness, it is better to use a plastic film.

The aforementioned plastic film includes, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyterephthalic acid Ethylene glycol film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc.

The thickness of the aforementioned separator is usually 5~200μm, preferably about 5~100μm. If necessary, mold release, antifouling treatment, or coating type using silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based mold release agents, silica powder, etc., can be used on the aforementioned separators. , Kneading type, vapor deposition type and other anti-static treatment. In particular, by appropriately performing peeling treatments such as silicone treatment, long-chain alkyl treatment, and fluorine treatment on the surface of the separator, the peelability from the adhesive layer can be further improved.

The thickness of the rubber-based adhesive layer of the present invention is as described above.

(2) Manufacturing method 2

The irradiation of the aforementioned active energy rays is usually performed on the coating layer obtained by applying the aforementioned rubber-based adhesive composition to various supports and the like. In addition, the above-mentioned active energy rays can be irradiated directly after irradiating the coating layer (other members are not attached), or after attaching various members such as optical films such as separators or glass to the coating layer. When irradiating after bonding the aforementioned optical film or various members, active energy rays can be irradiated through the optical film or various members, or active energy rays can be irradiated from the peeled surface after peeling off the optical film or various members.

As an example, the method of applying the rubber-based adhesive composition can be the same as that of the manufacturing method 1 described above.

When the coating layer of the rubber-based adhesive composition is irradiated with active energy rays, when the rubber-based adhesive composition contains an organic solvent as a diluent, it can be dried by heating after coating and before the active energy ray is irradiated. It is better to remove the solvent, etc.

The aforementioned heating and drying temperature is not particularly limited, but from the viewpoint of reducing residual solvent, it is preferably about 30°C to 90°C, and more preferably about 60°C to 80°C. The drying time can be appropriate and appropriate time. The aforementioned drying time is preferably about 5 seconds to 20 minutes, preferably 30 seconds to 10 minutes, and more preferably 1 minute to 8 minutes.

Examples of the aforementioned active energy rays include visible light, ultraviolet rays, electron beams, etc., but ultraviolet rays are also preferred among them.

The UV irradiation conditions are not particularly limited, and any appropriate conditions can be set corresponding to the composition of the rubber-based adhesive composition to be crosslinked, but for example, the cumulative amount of irradiation light is preferably ^{100 mJ/cm 2} to 2000 mJ/cm ^2.

The aforementioned supporting body may be the aforementioned one as an example.

The thickness or moisture permeability of the rubber-based adhesive layer obtained by the aforementioned manufacturing method is as described above.

4. Adhesive film

The adhesive film of the present invention is characterized by having a support composed of a plastic substrate, and the aforementioned rubber-based adhesive layer provided on at least one side of the support.

The method of forming a rubber-based adhesive layer on the aforementioned support may include coating the aforementioned rubber-based adhesive composition on the support, and then removing the solvent by heating and drying, etc., or by irradiating active energy rays on the support A rubber-based adhesive layer is formed.

The rubber-based adhesive composition, the rubber-based adhesive layer, and the manufacturing method thereof are as described above.

The aforementioned plastic substrate is not particularly limited, as long as it can be formed into a sheet or film shape, for example: polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene Ethylene, ethylene. Propylene copolymer, ethylene. 1-Butene copolymer, ethylene. Vinyl acetate copolymer, ethylene. Ethyl acrylate copolymer, ethylene. Polyolefin film such as vinyl alcohol copolymer, polyester film such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyacrylate film, polystyrene film, nylon 6. Nylon 6,6, polyamide films such as some aromatic polyamides, polyvinyl chloride films, polyvinylidene chloride films, polycarbonate films, etc.

The thickness of the aforementioned film is usually around 5~200μm, preferably around 10~100μm.

If necessary, mold release and antifouling treatment, acid treatment, alkali treatment, etc. using silicone, fluorine, long-chain alkyl, or fatty acid amide-based mold release agents, silica powder, etc., can also be used on the plastic substrate , Primer treatment, corona treatment, plasma treatment, ultraviolet treatment and other easy-to-adhesive treatments, coating type, kneading type, vapor deposition type and other anti-static treatments.

The adhesive film of the present invention can be used as various surface protection sheets, and can also be used as a peelable sheet with less pollution. in this way The re-peeling sheet is suitable for use in anti-reflective films, anti-reflective glass, etc., which are easily contaminated, as a re-peeling sheet with little pollution. In addition, it is more suitable for use by using a rubber-based matrix polymer with a low polydispersity and further cross-linking.

5. Optical film with adhesive layer

The optical film with a rubber-based adhesive layer of the present invention is characterized by having an optical film and the rubber-based adhesive layer provided on the optical film.

In the method of forming a rubber-based adhesive layer on the optical film, after coating the rubber-based adhesive composition on the optical film, the solvent is removed by heating and drying, etc., or by irradiating active energy rays on the optical film A rubber-based adhesive layer is formed. Furthermore, as described above, by forming a rubber-based adhesive layer on a support or the like, and transferring the rubber-based adhesive layer to an optical film, an optical film with the rubber-based adhesive layer can also be formed. In this case, the peeled-off sheet used in the production of the aforementioned rubber-based adhesive layer-attached optical film can be directly used as a separate part of the rubber-based adhesive layer-attached optical film, which can simplify the manufacturing steps.

The rubber-based adhesive composition, the rubber-based adhesive layer, and the manufacturing method thereof are as described above.

The aforementioned optical film can be used to form users of various image display devices such as liquid crystal display devices, and the types thereof are not particularly limited. The optical film can be a polarizing film as an example. The polarizing film is generally one with a protective film on one or both sides of the polarizer. However, in the present invention, from the viewpoint of thinning, a single-sided protective polarizing film is preferred.

The polarizer is not particularly limited, and various types can be used. Examples of polarizers include: polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, and ethylene. Hydrophilic polymer films such as partially saponified films of vinyl acetate copolymer adsorb iodine or dichroic dyes and then uniaxially stretched, dehydrated polyvinyl alcohol or dehydrochloric acid treatment of polyvinyl chloride Polyene-based alignment films such as materials. Among them, a polarizer composed of a polyvinyl alcohol-based film and dichroic substances such as iodine is also preferred. The thickness of the polarizers is not particularly limited, but it is generally about 5 to 80 μm.

A polarizer that is uniaxially stretched with a polyvinyl alcohol-based film dyed with iodine can be produced by, for example, immersing polyvinyl alcohol in an iodine aqueous solution to dye it, and then stretch it to 3 to 7 times the original. If necessary, it can also be immersed in an aqueous solution such as potassium iodide that may contain boric acid, zinc sulfate, zinc chloride, and the like. If necessary, the polyvinyl alcohol-based film may be immersed in water and washed before dyeing. By washing the polyvinyl alcohol film with water, in addition to cleaning the dirt or anti-caking agent on the surface of the polyvinyl alcohol film, it also has the effect of swelling the polyvinyl alcohol film to prevent uneven dyeing. The extension can be performed after iodine dyeing, or it can be extended while dyeing, or dyed with iodine after extension. It can also be extended in aqueous solutions or water baths such as boric acid or potassium iodide.

In addition, from the viewpoint of thinning, it is preferable to use a thin polarizer with a thickness of 10 μm or less. From the viewpoint of thinning, the thickness is preferably 1~7μm. Such a thin polarizer has little unevenness in thickness, is excellent in visual confirmation, and has little dimensional change, so it is excellent in durability. In addition, the thickness of the polarizing film also contributes to thinning.

Representative thin polarizers, for example: Japanese special Japanese Patent Application Publication No. 51-069644, Japanese Patent Application Publication No. 2000-338329, International Patent Publication No. 2010/100917 Manual, Japanese Patent Application Publication No. 2014-59328, or Japanese Patent Application Publication No. 2012-73563 The described thin polarizing film. These thin polarizing films can be obtained by a manufacturing method including the following steps: a step of extending a polyvinyl alcohol-based resin (hereinafter, also referred to as a PVA-based resin) layer and a resin substrate for stretching in the state of a laminate and a dyeing step. As long as it is this manufacturing method, even if the PVA-based resin layer is thin, it can be supported by the resin base material for stretching, and it can be stretched without defects such as breakage caused by stretching.

From the point of view that the polarization performance can be improved by stretching at high magnification even in the manufacturing method including the stretching step and the dyeing step in the state of a laminate, the aforementioned thin polarizing film is as in International Publication No. 2010/100917 Manual, Or Japanese Patent Laid-Open No. 2014-059328 or Japanese Patent Laid-Open No. 2012-073563 is preferably obtained by the method of preparation including the step of extending in a boric acid aqueous solution, especially by Japanese Patent Laid-Open No. 2014-059328 Or it is preferably obtained by the manufacturing method including the step of subsidizing ground-to-air spreading before spreading in a boric acid aqueous solution as described in Japanese Patent Laid-Open No. 2012-073563.

The material for forming the protective film provided on one side or both sides of the aforementioned polarizer is preferably one that is excellent in transparency, mechanical strength, thermal stability, moisture interception, and isotropy. Examples include polyester polymers such as polyethylene terephthalate or polyethylene naphthalate, cellulose polymers such as diacetyl cellulose or triacetyl cellulose, polymethylmethacrylate Acrylic polymers such as esters, polystyrene or acrylonitrile (styrene copolymer (AS resin), etc.) Styrene-based polymers, polycarbonate-based polymers, etc. In addition, polyethylene, polypropylene, polyolefins with cyclic or norbornene structures, polyolefin polymers such as ethylene (propylene copolymers, vinyl chloride polymers, nylon or aromatic polyamides, etc.) Materials, imine-based polymers, turbidity-based polymers, polyether turbidity-based polymers, polyetheretherketone-based polymers, polyphenylene sulfide-based polymers, vinyl alcohol-based polymers, and chlorinated vinylidene-based polymers , Vinyl butyral polymers, aryl ester polymers, polyoxymethylene polymers, epoxy polymers, or blends of the aforementioned polymers, etc. can also be used as the polymer forming the aforementioned protective film For example, it is also possible to form a protective film with a hardened layer of thermosetting and ultraviolet curing resins such as acrylic, urethane, acrylic urethane, epoxy, and silicone resins. On both polarizers When the protective film is set on the side, the protective film made of the same polymer material can be used on the front and the back, or the protective film made of different polymer materials can also be used.

The thickness of the protective film can be appropriately determined. Generally speaking, it is about 1 to 500 μm in terms of workability such as strength, handling properties, and film properties.

The aforementioned polarizer and protective film are usually tightly adhered through water-based adhesives and the like. Examples of water-based adhesives include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl latex-based adhesives, water-based polyurethanes, water-based polyesters, and the like. In addition to the foregoing, the adhesive for the polarizer and the protective film may be an ultraviolet curable adhesive, an electron beam curable adhesive, etc. as examples. Compared with the aforementioned various protective films, the adhesive for electron beam hardening polarizing films shows better adhesion. In addition, the adhesive used in the present invention may contain a metal compound filler.

On the side of the polarizer that is not attached to the aforementioned protective film, it can also be Implement hard coating or anti-reflection treatment, treatment for the purpose of anti-sticking, diffusion or anti-glare.

For example, as shown in FIG. 1, when the polarizing film 2 is a single-sided protective polarizing film having a protective film 5 on only one side of the polarizer 4, the adhesive layer-attached polarizing film 1 of the present invention uses the aforementioned rubber-based adhesive layer 3 is preferably formed on the side of the polarizer 4 without the protective film 5 (ie, the side of the polarizer 4) (that is, it is better to laminate the rubber-based adhesive layer 3, the polarizer 4, and the protective film 5 in this order). At this time, the aforementioned polarizer 4 and the adhesive layer 3 are not necessarily in contact, but from the viewpoint of remarkably exhibiting the effect of the present invention, such contact is preferable. With such a structure, it is possible to suppress the movement of moisture and the like to the polarizer, and it is possible to suppress the deterioration of the polarizer of the single-sided protective polarizing film.

In addition, the aforementioned polarizing film with the adhesive layer can also use a retardation film. For example, when a single-sided protective polarizing film is used as the polarizing film, as shown in Figure 2, the rubber-based adhesive layer 3 and retardation film are sequentially laminated. The film 6, the polarizer 4, and the protective film 5 are preferred.

The aforementioned retardation film is preferably a film that can function as a λ/4 plate. The in-plane retardation Re(550) of such retardation film measured with light with a wavelength of 550nm at 23°C is preferably 100~180nm, preferably 110~170nm, more preferably 120~160nm, and 135~155nm. good. The in-plane retardation Re can be obtained by Re=(nx-ny)×d (d: film thickness (nm)). The aforementioned retardation film that can function as a λ/4 plate can be laminated so that its slow axis is in an oblique direction (for example, 45° direction) with respect to the absorption axis of the polarizer.

In addition, a representative retardation film has a refractive index ellipse of nx>ny=nz, or nx>ny>nz. Here, nx is the surface The internal refractive index is the refractive index in the maximum direction (ie, the slow axis direction), ny is the refractive index in the direction perpendicular to the slow axis (ie, the fast axis direction) in the plane, and nz is the refractive index in the thickness direction. In addition, in this specification, ny=nz is not only strictly equal, but also includes substantially equal.

The Nz coefficient of the retardation film is preferably 0.9~2, preferably 1~1.5, and more preferably 1~1.3. Here, the Nz coefficient is obtained by Nz=Rth/Re. The aforementioned Rth is the retardation in the thickness direction, which is obtained by Rth=(nx-nz)×d (d: film thickness (nm)).

The aforementioned retardation film can be a well-known retardation film, to use a retardation film with a polymer or liquid crystal compound with reverse wavelength dispersion characteristics, or a retardation film laminated with a λ/2 plate and a λ/4 plate Film is better. By using these retardation films, circularly polarized light can be obtained in a wide wavelength range and an excellent color tone can be achieved.

The material for forming the retardation film laminated with the λ/2 plate and the λ/4 plate can use a polymer or a liquid crystal compound, but from the point of view of thinning, a liquid crystal compound is preferred.

In addition, in the present invention, a second retardation film whose refractive index characteristic shows the relationship of nz>nx≧ny can be used together with the aforementioned retardation film (also referred to as the first retardation film). By providing such a second retardation film, light incident from an oblique direction can sufficiently maintain the function of the λ/4 plate (first retardation film), and as a result, a very excellent reflection hue in an oblique direction can be achieved. The thickness direction retardation Rth(550) of the second retardation film is preferably -260nm~-10nm, preferably -200nm~-20nm, more preferably -180nm~-30nm, particularly preferably -180nm~-60nm .

In the first embodiment, the refractive index of the second retardation film shows a relationship of nx=ny. Here, "nx=ny" is not only the case where nx and ny are strictly equal, but also the case where nx and ny are substantially equal. Specifically, Re(550) is less than 10 nm. In other embodiments, the refractive index of the second retardation film shows a relationship of nx>ny. At this time, the in-plane retardation Re(550) of the second retardation film is preferably 10nm~150nm, more preferably 10nm~80nm. It is better that the refractive index of the second retardation film shows a relationship of nx>ny. By using such a retardation film, it is possible to better compensate for the geometric off-axis of the slow axis of the first retardation film as seen from the oblique direction, because the anti-reflection function in the oblique direction can be greatly improved. Furthermore, as described above, when nx and ny are substantially equal and when nx>ny, the slow axis can be expressed in the second retardation film. At this time, the slow axis of the second retardation film can be laminated to make it parallel or perpendicular to the absorption axis of the polarizer.

The second retardation film can be formed of any appropriate material. It is better to fix the liquid crystal layer arranged on the vertical plane. The liquid crystal material (liquid crystal compound) that can be vertically aligned can be a liquid crystal monomer or a liquid crystal polymer. Specific examples of the liquid crystal compound and the method of forming the liquid crystal layer include the liquid crystal compound and the method of forming described in [0020] to [0042] of Japanese Patent Laid-Open No. 2002-333642. At this time, the thickness is preferably 0.1 μm to 5 μm, preferably 0.2 μm to 3 μm. Since the liquid crystal layer can obtain the desired optical properties with an extremely thin thickness, the circular polarizing plate can be greatly thinned.

As another preferable specific example, the second retardation film may be a retardation film formed of a fumarate diester resin described in JP 2012-32784 A. At this time, the thickness is 5μm~50μm Preferably, 10μm~35μm is preferred. Since the retardation film formed of the fumarate diester-based resin has a wavelength dispersion characteristic close to a flat dispersion, it has the advantage of less hue change.

In addition, optical films other than the aforementioned polarizing film include, for example, reflective plates or semi-transmissive plates, retardation films other than the aforementioned retardation films (including 1/2 or 1/4 wavelength plates), viewing angle compensation films, and brightness enhancement films. Etc. as an optical layer used in forming liquid crystal display devices and the like. Among them, a brightness enhancement film can be preferably used as an optical film. These can be used alone as an optical film, but can be used in one layer or two or more layers of the aforementioned polarizing film in actual use.

In addition, an anchor layer or a transparent resin layer can be formed on the surface of an optical film or a polarizer, corona treatment, plasma treatment, and other easy bonding treatments can be applied to form an adhesive layer. In addition, easy bonding treatment can also be performed on the surface of the adhesive layer.

6. Optical components

The optical member of the present invention is characterized ^{by a film having a moisture permeability of 1 g/(m 2} .day) or less at 40° C. and 92% RH, and having the aforementioned rubber-based adhesive layer on at least one side of the film.

The method of forming the rubber-based adhesive layer on the aforementioned film, the rubber-based adhesive composition, and the rubber-based adhesive layer are as described above.

The aforementioned moisture permeability at 40°C and 92%RH is 1g/m ² . For thin films below day, barrier layers used in organic EL devices can be cited as examples. The barrier layer used in the organic EL element can include, for example: trifluoropolyethylene, polychloroethylene trifluoride (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic Formula polyolefins, ethylene-vinyl alcohol copolymers and other polymer layers, or laminates of these, and even the aforementioned polymer layers are coated with silicon oxide, silicon nitride, aluminum oxide, diamond-like carbon by sputtering and other film forming methods Those who wait for inorganic thin films, etc. The optical member having such a low moisture permeability film can be used in an organic EL device, specifically, it can be used as a sealing member of an organic EL device.

7. Image display device

The image display device of the present invention is characterized by including one or more selected from the group consisting of the polarizing film with the adhesive layer and the optical member. Examples of image display devices include liquid crystal display devices and organic EL display devices.

The image display device of the present invention only needs to include the optical film or optical member with the adhesive layer of the present invention, and other structures may be the same as those of the conventional image display device.

Since the image display device of the present invention includes the aforementioned optical film or optical member with the adhesive layer, it has high optical reliability.

Example

Hereinafter, the present invention will be explained in detail through examples, but the present invention is not limited by these examples. In addition, the parts and% in each example are based on weight.

Manufacturing example 1 (manufacturing of polarizing film (1))

To make a thin polarizing film, firstly, a laminate of 9μm thick polyvinyl alcohol (PVA) layer has been formed on an amorphous polyethylene terephthalate (PET) substrate by stretching at a temperature of 130°C. Air support extended to generate extended buildup body. Next, by dyeing the stretched laminate to produce a colored laminate, and by stretching the colored laminate in boric acid water at a stretching temperature of 65°C, a total stretch ratio of 5.94 times was generated including the stretched laminate integrated with the amorphous PET substrate Optical film laminate with 4μm thick PVA layer. Through such two-stage extension, an optical film laminate including a PVA layer with a thickness of 5 μm is generated. The optical film laminate system is structured such that the PVA layer that has been filmed on the amorphous PET substrate is highly aligned with PVA molecules, and The iodine adsorbed by dyeing is a highly unidirectionally aligned high-performance polarizing film (polarizer) in the form of polyiodide ion complexes.

On the surface of the polarizing film (polarizer, thickness: 5μm) of the optical film laminate of the polarizer, a polyvinyl alcohol-based adhesive was applied to the surface of the polarizer so that the thickness of the adhesive layer was 0.1μm, and a protective film (the thickness of the After corona treatment is applied to a 20μm (meth)acrylic resin film with a lactone ring structure, it is dried at 50°C for 5 minutes. Next, the amorphous PET substrate was peeled off to produce a single protective polarizing film (polarizing film (1)) using a thin polarizer.

Manufacturing example 2 (manufacturing of polarizing film (2))

Between rolls with different speed ratios, the polyvinyl alcohol film with a thickness of 30μm is dyed in an iodine solution with a concentration of 0.3% at 30°C for 1 minute, and the other side is stretched to 3 times. After that, while immersing in an aqueous solution containing 4% boric acid and 10% potassium iodide at 60°C for 0.5 minutes, the side was stretched to a total stretching ratio of 6 times. Next, it was immersed in an aqueous solution containing 1.5% potassium iodide at 30°C for 10 seconds and washed, and then dried at 50°C for 4 minutes to obtain a polarizer with a thickness of 12 μm. Use polyvinyl alcohol-based adhesive on the polarizer Laminate a 25μm triacetyl cellulose film with a thickness of 25μm, which is hard-coated on one side and saponified on the reverse side, and a 13μm cycloolefin resin film is laminated on the reverse side of the polarizer to make a double-protected polarizing film (polarizing film ( 2)). The structure of the polarizing film (2) is hard coating/triacetyl cellulose film/adhesive layer/polarizer/adhesive layer/cycloolefin resin film.

Production Example 3 (Production of the first retardation film)

Respectively, 37.5 parts by mass of isosorbide (ISB), 91.5 parts by mass of 9,9-bis[4-(2-hydroxyethoxy)phenyl] pyridium (BHEPF), and polyethylene glycol (PEG) with an average molecular weight of 400 8.4 parts by mass, 105.7 parts by mass of diphenyl carbonate (DPC), and 0.594 parts by mass of cesium carbonate (0.2% by mass aqueous solution) as a catalyst are put into the reaction vessel, and the heat carrier temperature of the reaction vessel is set under a nitrogen atmosphere. The temperature is 150°C, and the raw materials are dissolved while stirring as necessary (about 15 minutes) as the first step of the reaction.

Next, the pressure in the reaction vessel was set to 13.3 kPa from normal pressure, while the heat carrier temperature of the reaction vessel was raised to 190° C. within 1 hour, the phenol produced was extracted to the outside of the reaction vessel. After maintaining the temperature in the reaction vessel at 190°C for 15 minutes, set the pressure in the reaction vessel to 6.67 kPa, raise the temperature of the heat carrier of the reaction vessel to 230°C within 15 minutes, and extract the generated phenol to the outside of the reaction vessel As a second stage step. As the stirring torque of the stirrer increased, the temperature was raised to 250°C within 8 minutes. The phenol produced was further removed, and the pressure in the reaction vessel was reduced to 0.200kPa or less. After reaching the predetermined stirring torque, the reaction is terminated. The reactant produced is extruded into water and then granulated. The content is obtained at the ratio of BHEPF/ISB/PEG=42.9 mol%/52.8 mol%/4.3 mol% Originated from Yuji Polycarbonate resin A which is a unit composed of a hydroxy compound. The obtained polycarbonate resin A had a glass transition temperature of 126°C and a reduced viscosity of 0.372 dL/g. After drying the obtained polycarbonate resin A in vacuum at 80°C for 5 hours, a single-screw extruder (screw diameter: 25mm, cylinder setting temperature: 220°C, manufactured by Isuzu Chemical Industries Co., Ltd.), T-die (Width: 300mm, set temperature: 220°C), chill roll (set temperature: 120~130°C), and coiler's film forming device to produce polycarbonate resin film with a length of 3m, a width of 300mm, and a thickness of 120μm. The water absorption rate of the obtained polycarbonate resin film was 1.2%.

The obtained polycarbonate resin film was cut into a length of 300 mm and a width of 300 mm, and longitudinally stretched at a temperature of 136° C. and a magnification of 2 times using a laboratory stretcher KARO IV (manufactured by Bruckner) to obtain a retardation film. The Re (550) of the obtained retardation film is 141 nm, and the Rth (550) is 141 nm (nx: 1.5969, ny: 1.5942, nz: 1.5942), and exhibits a refractive index characteristic of nx>ny=nz. In addition, the Re(450)/Re(550) of the obtained retardation film was 0.89 (in addition, the retardation variation obtained by the environmental test was 5 nm).

Production Example 4 (Production of the second retardation layer (second retardation film))

烯系樹脂薄膜，商品名：ZEONEX，日本ZEON(股)製)後，藉由在80℃下加熱乾燥4分鐘使液晶配向。對該液晶層照射紫外線使液晶層硬化，藉此於基材上形成構成第2相位差層的液晶固化層(厚度：0.58μm)。該層之Re(550)係0nm，Rth(550)係-71nm(nx：1.5326、ny：1.5326、nz：1.6550)，呈現nz>nx=ny之折射率特性。 20 parts by weight of the side chain liquid crystal polymer shown in the following chemical formula (I) (the numbers 65 and 35 in the formula show the molar% of the monomer unit, which is expediently expressed as the weight average molecular weight of the block polymer: 5000) . 80 parts by weight of polymerizable liquid crystal (trade name: Paliocolor LC242, manufactured by BASF Corporation) showing a nematic liquid crystal phase and 5 parts by weight of a photopolymerization initiator (trade name: IRGACURE907, manufactured by Chiba Specialty Chemicals) dissolved in cyclopentanone 200 parts by weight to prepare a liquid crystal coating liquid. Then, the coating solution was applied to the substrate film using a bar coater (to reduce

After the olefin-based resin film, trade name: ZEONEX, manufactured by ZEON (Japan), the liquid crystal was aligned by heating and drying at 80°C for 4 minutes. The liquid crystal layer was irradiated with ultraviolet rays to harden the liquid crystal layer, thereby forming a liquid crystal cured layer (thickness: 0.58 μm) constituting the second retardation layer on the substrate. The Re(550) of this layer is 0nm, Rth(550) is -71nm (nx: 1.5326, ny: 1.5326, nz: 1.6550), showing a refractive index characteristic of nz>nx=ny.

Production Example 5 (Production of retardation film A)

After bonding the second retardation layer (liquid crystal cured layer) obtained in Production Example 4 to the first retardation film obtained in Production Example 3 through an acrylic adhesive, the substrate film is removed to obtain a transfer on the first retardation film A laminate with a cured liquid crystal layer (retardation film A). The structure of the obtained retardation film A was a first retardation film/acrylic adhesive layer/second retardation layer. The Re (550) of the obtained retardation film A is 141 nm, and the Rth (550) is 70 nm.

Manufacturing example 6 (manufacturing of single protective polarizing film with retardation film)

Single protection polarized light obtained in manufacturing example 1 through polyvinyl alcohol-based adhesive The first retardation film of the retardation film A obtained in Production Example 5 was bonded to the polarizing film (polarizer) side of the film (polarizing film (1)). Here, the slow axis of the composite retardation film A is 45° in the counterclockwise direction with respect to the absorption axis of the polarizer to produce a single-protection polarizing film with retardation film (polarizing film (3)). The structure of the polarizing film (3) is protective film/adhesive layer/polarizer/adhesive layer/retardation film A.

Example 1

(Preparation of rubber-based composition)

A toluene solution (solid content: 13% by weight) of polyisobutylene (trade name: OPPANOL N50, Mw: 560,000, Mn: 240,000, Mw/Mn: 2.3, manufactured by BASF Corporation) was adjusted to prepare a rubber adhesive composition (solution) .

(Formation of rubber adhesive sheet)

The obtained adhesive composition (solution) was applied to the release-treated surface of a 38μm thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Plastics Co., Ltd.) that was subjected to silicone release treatment on one side to form a coating layer . Next, the coating layer was dried at 120°C for 3 minutes to form an adhesive layer, and an adhesive sheet with an adhesive layer thickness of 50 μm was produced. In addition, a 38μm-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) was pasted on the adhesive surface of the adhesive sheet with the silicone peeling treatment on one side, so that the peeling treatment surface and the adhesive layer Meet. The polyester film coated on both sides of the adhesive layer functions as a release liner (separator).

Examples 2, 3

Except for the polyisobutylene (OPPANOL N50) used in Example 1 Except for changing to the polyisobutylene described in Table 1, a rubber-based adhesive sheet was produced in the same manner as in Example 1.

Example 4

(Preparation of rubber-based composition)

An adhesive composition (solution) was prepared, and 100 parts by weight of polyisobutylene (trade name: OPPANOL N50, Mw: 560,000, Mn: 240,000, Mw/Mn: 2.3, manufactured by BASF Corporation) was blended as a tackifier. A toluene solution (adhesive solution) of 10 parts by weight of hydrogenated terpene phenol (softening point: 135°C, hydroxyl value: 160 fully hydrogenated terpene phenol) was adjusted to a solid content of 13% by weight.

Except that the rubber-based adhesive composition obtained above was used and the film thickness was 25 μm, a rubber-based adhesive sheet was produced in the same manner as in Example 1.

Examples 5~7

Except that the type of polyisobutylene, the amount of fully hydrogenated terpene phenol added, and the film thickness were changed as described in Table 1, a rubber-based adhesive sheet was produced in the same manner as in Example 4.

Example 8

(Preparation of rubber-based composition)

Fully hydrogenated terpene phenol (softening point: 135 ℃, hydroxyl value: 160 fully hydrogenated terpene phenol) 5 parts by weight, as a multifunctional radical polymerizable compound tricyclodecane dimethanol diacrylate (trade name: NK ester A-DCP, bifunctional acrylate, molecular weight: 304, 5 parts by weight, manufactured by Shinnakamura Chemical Industry Co., Ltd., hydrogen abstraction type photopolymerization initiator, diphenyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) One part of the toluene solution (adhesive solution) was adjusted to have a solid content of 13% by weight to prepare a rubber-based adhesive composition (solution).

(Formation of rubber adhesive sheet)

The rubber-based adhesive composition (solution) obtained was applied to the release-treated surface of a polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Plastics Co., Ltd.) with a thickness of 38 μm that was subjected to a silicone release treatment on one side to form a coating. Cloth layer. Next, the coating layer was dried at 80°C for 3 minutes to form a rubber-based adhesive layer, and an adhesive sheet having a rubber-based adhesive layer thickness of 50 μm was produced. In addition, a 38μm-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Plastics Co., Ltd.) was bonded to the adhesive surface of the adhesive sheet with the silicone peeling treatment on one side. The adhesive layers are connected. The polyester film coated on both sides of the rubber-based adhesive layer functions as a release liner (separator).

Ultraviolet rays are irradiated at room temperature to obtain a rubber-based adhesive sheet composed of a separator/rubber-based adhesive layer/separator. The aforementioned ultraviolet rays are irradiated with a light amount of 1000 mJ/cm ² in the UVA region.

Examples 9~13

Except that the composition described in Table 1 was adopted, a rubber-based adhesive sheet was produced in the same manner as in Example 8.

Comparative example 1~3

Except that the composition described in Table 1 was adopted, a rubber-based adhesive sheet was produced in the same manner as in Example 1.

Comparative example 4

(Production of acrylic adhesive sheet)

Put 99 parts by weight of butyl acrylate (BA) and 1 part by weight of 4-hydroxybutyl acrylate (4HBA) as a monomer component into a separable flask equipped with a thermometer, a stirrer, a reflux cooling tube and a nitrogen introduction tube, as a polymerization After 0.2 parts by weight of azobisisobutyronitrile as the initiator and ethyl acetate as the polymerization solvent were used to make the solid content 20%, nitrogen gas was flowed in, and nitrogen substitution was performed for about 1 hour while stirring. After that, the flask was heated to 60°C and reacted for 7 hours to obtain an acrylic polymer with a weight average molecular weight (Mw) of 1.1 million. Trimethylolpropane toluene diisocyanate (trade name: CORONATE L, manufactured by Japan Polyurethane Industry Co., Ltd.) as an isocyanate-based crosslinking agent was added to the aforementioned acrylic polymer solution (100 parts by weight of solid content) ) 0.8 parts by weight of silane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 parts by weight to prepare an acrylic adhesive composition.

The obtained acrylic adhesive composition was applied to the release-treated surface of a 38 μm-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Plastics Co., Ltd.) that was subjected to silicone release treatment on one side to form a coating layer. Next, the coating layer was dried at 120°C for 3 minutes to form an adhesive layer, and an adhesive sheet with an adhesive layer thickness of 50 μm was produced. In addition, a 38μm-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) was pasted on the adhesive surface of the adhesive sheet with the silicone peeling treatment on one side, so that the peeling treatment surface and the adhesive layer Connected to obtain an acrylic adhesive sheet. The polyester film coated on both sides of the adhesive layer functions as a release liner (separator).

The following evaluations were performed on the adhesive compositions and adhesive sheets obtained in the examples and comparative examples. Table 1 shows the evaluation results.

<Durability>

The release liner on one side of the adhesive sheet obtained in the Examples and Comparative Examples was peeled off to expose the adhesive surface, and the polarizer of the polarizing film (1) obtained in Manufacturing Example 1 was attached through the adhesive surface. Then, the release liner on the other side was peeled off to obtain a measurement sample 1 (single protective polarizing film).

In addition, the release liner on one side of the adhesive sheet obtained in the Examples and Comparative Examples was peeled to expose the adhesive surface, and the adhesive sheet was bonded to the cycloolefin resin film of the polarizing film (2) through the adhesive surface. Then, the release liner on the other side was peeled off to obtain a measurement sample 2 (dual protective polarizing film).

In addition, the release liner on one side of the adhesive sheet obtained in the Examples and Comparative Examples was peeled to expose the adhesive surface, and the adhesive sheet was bonded to the retardation film A of the polarizing film (3) through the adhesive surface. Then, the release liner on the other side was peeled off to obtain a measurement sample 3 (single protective polarizing film with retardation film).

The measurement samples 1 to 3 obtained above were respectively attached to the glass plate, and the state after being put into the 85°C environment for 500 hours was observed by visual inspection or a magnifying glass (20 times). Evaluate based on the following evaluation criteria.

⊚: It is confirmed with a magnifying glass that no defects (foaming, peeling, etc.) have occurred.

○: The defects could not be confirmed visually, but some defects occurred when confirmed with a magnifying glass that would not hinder the use.

×: Defects can be confirmed visually.

<From the glue>

Use a magnifying glass (20 times) to observe the state of the ends of the measurement samples 1 to 3 obtained from the durability test after being placed in an environment of 85°C for 500 hours. Evaluate based on the following evaluation criteria.

◎: It is not possible to visually confirm the occurrence of glue separation, but when confirmed with a magnifying glass, there is a slight separation of glue which is not harmful to use.

○: It can be visually confirmed that the release of glue within the range that does not cause defects can be confirmed.

×: It can be confirmed that the end of the polarizing plate deviates from the end of the glue, which is a defect.

<Humidity Permeability>

The release liner on one side of the adhesive sheet obtained in the example and the comparative example was peeled off to expose the adhesive surface, and the adhesive sheet was attached to the triacetyl cellulose film (TAC film, thickness 25μm, KONICA MINOLTA) through the adhesive surface. (Share) system). And peel off the release liner on the other side to obtain a sample for measurement.

Next, using this sample for measurement, the moisture permeability test method (cylinder flat plate method, according to JIS Z 0208) was measured under the following conditions to measure the moisture permeability (water vapor permeability).

Measuring temperature: 40℃

Relative humidity: 92%

Measurement time: 24 hours

In addition, a constant temperature and humidity bath was used for the measurement.

The labels in Table 1 are as follows.

<Polyisobutylene>

OPPANOL N50: Polyisobutylene (Mw: 560,000, Mn: 240,000, Mw/Mn: 2.3, manufactured by BASF Corporation)

OPPANOL N80: Polyisobutylene (Mw: 1,050,000, Mn: 440,000, Mw/Mn: 2.4, manufactured by BASF Corporation)

OPPANOL N100: Polyisobutylene (Mw: 1,550,000, Mn: 530,000, Mw/Mn: 2.9, manufactured by BASF Corporation)

OPPANOL B50: Polyisobutylene (Mw: 535,000, Mn: 111,458, Mw/Mn: 4.8, manufactured by BASF Corporation)

OPPANOL B80: Polyisobutylene (Mw: 1,150,000, Mn: 239,583, Mw/Mn: 4.8, manufactured by BASF Corporation)

OPPANOL B100: Polyisobutylene (Mw: 1,680,000, Mn: 365,217, Mw/Mn: 4.6, manufactured by BASF Corporation)

<Polymers other than these>

Acrylic resin: Acrylic adhesive composition obtained in Comparative Example 4

<Tackifier>

Fully hydrogenated terpene phenol: a fully hydrogenated terpene phenol with a softening point of 160°C and a hydroxyl value of 60

<Multifunctional radical polymerizable compound>

A-DCP: Tricyclodecane dimethanol diacrylate (trade name: NK ester A-DCP, bifunctional acrylate, molecular weight: 304, manufactured by Shinnakamura Chemical Industry Co., Ltd.)

DCP: Tricyclodecane dimethanol dimethacrylate (trade name: NK ester, DCP, bifunctional methacrylate, molecular weight: 332, manufactured by Shinnakamura Chemical Industry Co., Ltd.)

<Photoinitiator>

Diphenyl ketone: hydrogen abstraction type photopolymerization initiator

1‧‧‧Polarizing film with adhesive layer

2‧‧‧Polarizing film

3‧‧‧Rubber adhesive layer

4‧‧‧Polarizer

5‧‧‧Protection film

Claims (13)

A rubber-based adhesive composition comprising a rubber-based matrix polymer. The rubber-based adhesive composition is characterized in that: the rubber-based matrix polymer contains an isobutylene-based polymer, and the weight-average molecular weight of the isobutylene-based polymer is 1 million Above, and the polydispersity (weight average molecular weight/number average molecular weight) is less than 3; the 50μm rubber adhesive layer formed from the aforementioned rubber adhesive composition has a moisture permeability of 50g at 40°C and 92%RH /(m ² ．day) or less. Such as the rubber-based adhesive composition of claim 1, which contains a tackifier. The rubber-based adhesive composition of claim 2, wherein the aforementioned tackifier is selected from the group consisting of a tackifier containing a terpene skeleton, a tackifier containing a rosin skeleton, and these hydrides At least one kind of tackifier. The rubber-based adhesive composition of claim 2, wherein the softening point of the aforementioned tackifier is 90°C or higher. The rubber-based adhesive composition according to any one of claims 1 to 4, which contains a hydrogen abstraction type photopolymerization initiator. A rubber-based adhesive layer characterized by being formed of the rubber-based adhesive composition according to any one of claims 1 to 5. An adhesive film characterized by having: a support body, which is composed of a plastic base material; and the rubber-based adhesive layer according to claim 6, which is located to the end of the support body Less one-sided. An optical film with a rubber-based adhesive layer, which is characterized by having: an optical film; and the rubber-based adhesive layer according to claim 6, which is located on at least one side of the optical film. According to claim 8, the optical film with a rubber-based adhesive layer, wherein the aforementioned optical film is a polarizing film having a protective film on at least one side of a polarizer. For example, the optical film with a rubber-based adhesive layer of claim 9, wherein the aforementioned polarizing film is a single-sided protective polarizing film with a protective film on only one side of the polarizer, and the aforementioned rubber-based adhesive layer and polarizer are laminated in this order Pieces, protective film. For example, the optical film with a rubber-based adhesive layer of claim 10, wherein the optical film with a rubber-based adhesive layer further includes a retardation film, and the rubber-based adhesive layer, the retardation film, and the polarizer are laminated in this order , Protective film. An optical member characterized by having: a film whose moisture permeability at 40° C. and 92% RH is 1 g/(m ² .day) or less; and the rubber-based adhesive layer according to claim 6, which is located on the film It is at least one-sided. An image display device, characterized in that it contains at least one rubber-based adhesive such as any one of claims 8 to 11 The optical film of the adhesive layer, or the optical member as claimed in claim 12.

Images