JP5616187B2 - Molded body and resin composition for molded body - Google Patents

Description

The present invention relates to a molded body and a resin composition for a molded body. More specifically, the present invention relates to a molded body useful as an optical member / part in various optical devices and the like and a resin composition for the molded body.

In a non-light emitting display device such as a liquid crystal display, illumination is performed by a backlight installed on the back surface of the display panel. Examples of such a backlight include an edge light type backlight including a light source such as a cold cathode tube or an LED (Light Emitting Diode) and a light guide plate. Conventionally, in such an edge light type backlight, there is a gap between the light source and the light guide plate, and light incident from the light source is reflected by the end face of the light guide plate. There was a problem that decreased. Further, in order to prevent the display panel from being damaged, a device for providing a protective panel on the front surface of the display device is often used. Usually, a space is provided between the protective panel and the display panel by a spacer, and the shock is dispersed and absorbed by the air layer and the protective panel. There is a problem that light is scattered due to a difference in refractive index from the panel or the protective panel, and the visibility of the image is lowered. Therefore, in order to solve these problems, a technique for reducing optical loss by interposing a transparent member in the above-described gap has been researched and developed.

As a technique for reducing light loss in an edge-light type backlight, it is disclosed to provide a transparent adhesive layer that closely attaches both between a light source and a light guide plate (see Patent Document 1). As the agent layer, an acrylic pressure-sensitive adhesive that does not absorb visible light is exemplified. Further, by joining the light source and the light guide plate through a transparent elastic body, an air layer is not formed even if there are some unevenness on the joint surface, and the light source and the light guide plate can improve the light introduction efficiency. Is disclosed (see Patent Document 2). Patent Document 2 describes the use of a silicone resin as an elastic body. However, a silicone resin usually has insufficient transparency and has a problem that the light transmission property is lowered. Therefore, a silicone resin excellent in transparency suitable for optical applications has been studied. For example, Patent Document 3 discloses a silicone resin obtained using a silsesquioxane derivative.

On the other hand, as a technique for reducing light loss in a display device provided with a protection panel, a curable resin composition having a constant curing shrinkage rate is applied to the gap between the image display unit and the protection unit, and then cured. It is disclosed that a cured resin layer is interposed between the image display unit and the protection unit (see Patent Document 4).

JP-A-6-308487 Japanese Patent Laid-Open No. 9-50704 JP 2006-233154 A JP 2008-282000 A

As described above, various techniques for reducing optical loss due to the presence of voids have been studied, but these conventional technologies ensure the durability of the resin interposed in the voids and the visibility of the image, There was room for improvement in terms of reducing optical loss. Specifically, for example, in an embodiment in which an adhesive layer is provided in the gap as in Patent Document 1, optical transmission is caused by deterioration or peeling of the adhesive layer due to moisture or temperature changes in the use environment. The display portion may be deformed due to the deterioration of the properties or the adhesive layer may expand or contract, resulting in poor display. Moreover, the silicone resin as described in Patent Document 2 has a problem that the transparency is insufficient and the light transmission property is low. Although a silicone resin with improved transparency as in Patent Document 3 has been studied, there is a possibility that the adhesiveness is not sufficient and the light loss cannot be sufficiently reduced. Moreover, since a silicone resin is generally expensive, it is disadvantageous for reducing the cost of the member. Moreover, in the method of forming a cured resin layer by applying and curing a resin composition in the gap as in Patent Document 4, the display panel is deformed by stress caused by curing shrinkage, the alignment disorder of the liquid crystal material, etc. There is a risk of causing a display defect. In addition, similarly to the case where the adhesive layer is provided, there is a problem that the light transmission property is lowered due to deterioration or peeling of the cured resin layer. As described above, the conventional technology has room for improvement in order to obtain a member having high durability and capable of reducing light loss without affecting image display.

The present invention has been made in view of the above situation, has moderate elasticity and adhesiveness, is excellent in transparency and durability, and can sufficiently suppress a decrease in light transmission property, It is an object of the present invention to provide a molded article suitable as a member such as a light transmission adhesive sheet interposed in a gap or the like existing in an optical apparatus such as a display device.

The inventor has studied various members for reducing light loss in a display device, and has focused on a molded body formed using an aliphatic (meth) acrylate oligomer and an aliphatic (meth) acrylate monomer as essential components. did. And it discovered that by using a specific aliphatic (meth) acrylate-based oligomer, the obtained molded article had appropriate tackiness and elasticity, and had excellent transparency and durability. Further, when such a molded body is interposed in the gap between the light source and the light guide plate in the backlight of the display device, the gap between the display panel and the protective panel, etc., the image display is affected. In addition, the inventors have found that the light loss due to unnecessary reflection can be sufficiently reduced and the reduction of the light transmission property can be suppressed.

That is, the present invention is a molded article formed from an aliphatic (meth) acrylate oligomer and an aliphatic (meth) acrylate monomer as essential components, and the aliphatic (meth) acrylate oligomer is included in the main chain. It has an aliphatic hydrocarbon group and has a non-hydrocarbon group in the main chain and / or side chain, and the aliphatic (meth) acrylate oligomer has a weight average molecular weight of 1,000 or more and 500,000 or less. It is a molded product characterized by being.
The present invention is also a composition for a molded article containing an aliphatic (meth) acrylate oligomer and an aliphatic (meth) acrylate monomer as essential components, the aliphatic (meth) acrylate oligomer mainly comprising It has an aliphatic hydrocarbon group in the chain and a non-hydrocarbon group in the main chain and / or side chain, and the aliphatic (meth) acrylate oligomer has a weight average molecular weight of 1,000 or more and 500,000. It is also the resin composition for molded objects characterized by the following.
The present invention is described in detail below.

<Aliphatic (meth) acrylate oligomer>
The aliphatic (meth) acrylate oligomer that forms the molded article of the present invention has a weight average molecular weight of 1,000 or more and 500,000 or less. If the weight average molecular weight is less than 1000, the resulting molded article becomes brittle and the handling properties are poor. On the other hand, when the weight average molecular weight exceeds 500,000, the viscosity of the resin composition containing the oligomer becomes too high, and molding and handling become difficult. Moreover, compatibility with the aliphatic (meth) acrylate monomer described later is deteriorated, and the transparency of the obtained molded article is not sufficiently increased. The weight average molecular weight is preferably 1500 or more and less than 450,000, and more preferably 2000 or more and less than 400000.
The weight average molecular weight can be measured by gel permeation chromatography (column: TSKgel SuperMultipore HZ-N 4.6 ^* 150, eluent: tetrahydrofuran, standard sample: TSK polystyrene standard).

The aliphatic (meth) acrylate oligomer has at least one (meth) acryloyl group in one molecule. From the viewpoint of obtaining a molded article having appropriate tackiness and elasticity, the oligomer is preferably a polyfunctional oligomer having two or more (meth) acryloyl groups in one molecule.

The aliphatic (meth) acrylate oligomer also has an aliphatic hydrocarbon group in the main chain and a non-hydrocarbon group in the main chain and / or side chain. When the oligomer has such a structure, the resulting molded article is excellent in transparency, durability, and adhesiveness. Non-hydrocarbon groups include, for example, carbon and carbon atoms in the structure such as urethane bonds (—O—C (═O) —N (H) —) and ester bonds (—O—C (═O) —). The site has at least one atom other than hydrogen and does not contain a hydrocarbon in the structure.
The aliphatic (meth) acrylate oligomer may have a non-hydrocarbon group only in one of the main chain and the side chain, or have a non-hydrocarbon group in both the main chain and the side chain. It may be.

In the form in which the aliphatic (meth) acrylate oligomer has a non-hydrocarbon group in the main chain, the main chain has an organic skeleton containing an aliphatic hydrocarbon group and a non-hydrocarbon group.
Examples of the organic skeleton having an aliphatic hydrocarbon group and a non-hydrocarbon group in the main chain include a urethane skeleton having an aliphatic hydrocarbon group (R) and a urethane bond (—O—C (═O ) -N (H) -R-); an ester skeleton having an aliphatic hydrocarbon group (R) and an ester bond (-O-C (= O) -R-); an aliphatic hydrocarbon group (R) One kind of ether skeleton having an ether bond (—O—R—); carbonate skeleton having an aliphatic hydrocarbon group (R) and a carbonate bond (—O—C (═O) —O—R—) Or 2 or more types are suitable. The ether skeleton includes an oxyalkylene skeleton (—RO—) composed of an oxyalkylene group.
The form of the aliphatic (meth) acrylate oligomer having a non-hydrocarbon group in the side chain is, for example, a (meth) acrylate (co) polymer skeleton composed of a (co) polymer of a (meth) acrylate monomer. The oligomer which has is mentioned.

The aliphatic (meth) acrylate oligomer has at least one skeleton selected from the group consisting of a urethane skeleton, an ester skeleton, an ether skeleton, a carbonate skeleton, and a (meth) acrylate (co) polymer skeleton. It is preferable. When the oligomer has such a skeleton, the obtained molded product is further excellent in transparency, durability, and adhesiveness.
More preferably, it has at least one skeleton selected from the group consisting of urethane skeleton, ester skeleton, ether skeleton and carbonate skeleton, and more preferably selected from the group consisting of urethane skeleton, ester skeleton and ether skeleton. Having at least one skeleton.
Even more preferably, it has two or more of a urethane skeleton, an ester skeleton, an ether skeleton, and a carbonate skeleton, that is, a polyurethane skeleton, a polyester skeleton, a polyether skeleton, or a polycarbonate skeleton.
More preferably, it has at least two skeletons selected from the group consisting of a urethane skeleton, an ester skeleton, an ether skeleton, and a carbonate skeleton, and particularly preferably a urethane skeleton and other organic compounds having a non-hydrocarbon group. A skeleton (for example, a (poly) ester skeleton, a (poly) ether skeleton, a (poly) carbonate skeleton, a (meth) acrylate (co) polymer skeleton, etc.). Most preferably, it has a urethane skeleton and a (poly) ester skeleton.

When the aliphatic (meth) acrylate oligomer contains a urethane skeleton in the main chain, the resulting molded article has excellent mechanical strength. Further, if the oligomer contains an ester skeleton, an ether skeleton or a carbonate skeleton in the main chain, in particular, a polyester skeleton, a polyether skeleton or a polycarbonate skeleton, the refractive index of the obtained molded product is used for the protective part of the display device. Acrylic resin (plate) and glass, glass used for light source lamps, acrylic resin (plate) and polycarbonate resin (plate) used for light guide plates, etc., close to the refractive index, thus increasing the light transmission efficiency Can do.
In the present specification, an aliphatic (meth) acrylate oligomer having a urethane skeleton in the main chain is also referred to as a urethane (meth) acrylate oligomer. In addition to the urethane skeleton, for example, an ester skeleton, an ether skeleton, etc. All aliphatic (meth) acrylate oligomers having other organic skeletons are classified as urethane (meth) acrylate oligomers. That is, for example, even if it has an ester skeleton or an ether skeleton in the molecule, it will be included in the urethane (meth) acrylate oligomer as long as it has a urethane skeleton.

The urethane (meth) acrylate oligomer can be obtained, for example, as a reaction product of an isocyanate compound obtained by reacting a polyol and diisocyanate and a (meth) acrylate monomer having a hydroxyl group. In addition, the reaction conditions normally used can be employ | adopted for this reaction.
Examples of the polyol include aliphatic polyester polyols, aliphatic polyether polyols, and aliphatic polycarbonate diols. When an aliphatic polyester polyol is used as the polyol, a urethane (meth) acrylate oligomer having a urethane skeleton and an ester skeleton in the structure is obtained. Similarly, when an aliphatic polyether polyol is used as the polyol, a urethane (meth) acrylate oligomer having a urethane skeleton and an ether skeleton in the structure is obtained, and when an aliphatic polycarbonate diol is used as the polyol, the urethane skeleton is included in the structure. And a urethane (meth) acrylate oligomer having a carbonate skeleton.

The method for producing the aliphatic polyester polyol is not particularly limited. For example, even when an aliphatic diol and an aliphatic dicarboxylic acid or an aliphatic dicarboxylic acid chloride are subjected to a polycondensation reaction, the diol or the dicarboxylic acid is esterified and transesterified. You may make it react. For this reaction, reaction conditions that are usually used can be employed.
Examples of the aliphatic diol include alkylene glycols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, and tetrapropylene glycol. It is preferable to use 1 type (s) or 2 or more types.
As the aliphatic dicarboxylic acid, it is preferable to use one or more of adipic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, maleic acid and the like.

As said aliphatic polyether polyol, 1 type (s) or 2 or more types of polyalkylene oxides, such as polyethylene oxide, polypropylene oxide, and ethylene oxide propylene oxide random copolymerization, can be used.
The aliphatic polycarbonate diol is produced by a transesterification reaction between a low-molecular carbonate compound and an aliphatic diol, and dimethyl carbonate can be used as the low-molecular carbonate compound. Examples of the aliphatic diol include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1 of aliphatic hydrocarbon diols such as 2-ethyl-1,3-hexanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol and polyoxyethylene glycol Species or two or more can be used.

As the diisocyanate, a linear or cyclic aliphatic diisocyanate can be used. Typical examples include hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylylene diisocyanate, and one or more of these can be used.
Examples of the (meth) acrylate monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, polyethylene glycol monoacrylate, pentaerythritol triacrylate, and dipentaerythritol peta. An acrylate etc. are mentioned, These 1 type (s) or 2 or more types can be used.

Specific examples of the urethane (meth) acrylate oligomer include, for example, EBECRYL 230, 270, 9260, 8296 (manufactured by Daicel Cytec); CN 9893, 9788, 983, 980, 981, 991, 9006, 9010, 9178 (manufactured by Sartomer) ); UF-8001G (manufactured by Kyoeisha); UV-7550B, 6100B, 3310B, 3200B, 3000B, 3700B, 3520TL, 3210EA (manufactured by Nippon Synthetic Chemical).
In addition, in this specification, the compound etc. in which the manufacture or sales company name was shown shall represent a brand name.

Among the aliphatic (meth) acrylate oligomers, an oligomer having a polyester skeleton (also referred to as a polyester (meth) acrylate oligomer) or an oligomer having a polyether skeleton (also referred to as a polyether (meth) acrylate oligomer). In addition to the ester skeleton and ether skeleton, the structure may have other skeletons other than the urethane skeleton, and may have a (meth) acryloxy group at the end of the structure or in the side chain. May be.
Specific examples of the polyester (meth) acrylate oligomer include CN294, CN2280, CN2270, CN2297, CN2470 (manufactured by Sartomer), and the like.

Among the ether skeletons in aliphatic (meth) acrylate oligomers having ether skeletons (for example, (poly) ether (meth) acrylate oligomers and urethane (meth) acrylate oligomers having ether skeletons), oxyalkylene skeletons (oxyalkylenes) The chain is not particularly limited. For example, an oxyalkylene chain having 1 to 30 carbon atoms is preferable.
In addition, the (meth) acrylate (co) polymer skeleton may have a structure obtained by (co) polymerizing an arbitrary aliphatic (meth) acrylate monomer, for example, an aliphatic (meth) acrylate oligomer. In addition, the structure etc. which (co) polymerize 1 type (s) or 2 or more types, such as the aliphatic (meth) acrylate type monomer mentioned later, etc. are mentioned. In order to obtain a molded article having excellent adhesiveness, an aliphatic chain hydrocarbon group having 4 or more carbon atoms is used as the aliphatic (meth) acrylate monomer forming the (meth) acrylate (co) polymer skeleton. Monomers having an aliphatic cyclic structure, monomers having a heterocyclic structure, monomers having a neopentyl structure and / or an alkylene glycol structure (oxyalkylene chain), and (meth) acryloyl groups and other polarities in one molecule It is preferable to use at least one monomer selected from the group consisting of monomers having a group. Furthermore, it is preferable that the (meth) acrylate-based (co) polymer skeleton contains 50% by mass or more of the preferable monomer with respect to 100% by mass of the total amount of monomers forming the (meth) acrylate-based (co) polymer skeleton. Specific examples of the preferable monomer are the same as the compounds exemplified in the aliphatic (meth) acrylate monomer described later.

The aliphatic (meth) acrylate oligomer may contain an aromatic ring in the structure as long as the light resistance and heat resistance of the molded article are not impaired. For example, when the total amount of the aliphatic (meth) acrylate oligomer is 100% by mass, the oligomer total amount is preferably included in a range where the mass ratio of the aromatic ring is 20% by mass or less. More preferably, it is 10 mass% or less, More preferably, it is 5 mass%, Most preferably, it is 0 mass%, ie, it does not contain an aromatic ring.

<Aliphatic (meth) acrylate monomers>
As the aliphatic (meth) acrylate monomer that forms the molded article of the present invention, an aliphatic (meth) acrylate compound other than the aliphatic (meth) acrylate oligomer can be used. In addition, the aliphatic (meth) acrylate compound used as a raw material of the said aliphatic (meth) acrylate type oligomer can also be used as the said aliphatic (meth) acrylate type monomer. That is, since the aliphatic (meth) acrylate compound used as a raw material does not correspond to the aliphatic (meth) acrylate oligomer itself, “aliphatic (meth) acrylate compound other than aliphatic (meth) acrylate oligomer” It corresponds to.

Examples of the aliphatic (meth) acrylate monomer include a monomer having an aliphatic chain hydrocarbon group having 4 or more carbon atoms, a monomer having an aliphatic cyclic structure, a monomer having a heterocyclic structure, a neopentyl structure and / or an alkylene glycol. A monomer having a structure (oxyalkylene chain) is preferably a monomer having a (meth) acryloyl group and another polar group in one molecule. The (meth) acrylate having such a structure is a monomer that gives a molded article excellent in durability (light resistance, heat resistance, and moisture resistance). More preferably, it is a monomer having a (meth) acryloyl group and another polar group in one molecule. Since such a monomer is excellent in compatibility with the aliphatic (meth) acrylate oligomer, the resulting molded article is excellent in transparency. Moreover, the moisture resistance of the obtained molded object can also be improved.

The aliphatic (meth) acrylate-based monomer may be either a polyfunctional monomer or a monofunctional monomer, but is preferably a monofunctional monomer. Thereby, the molded object which has moderate adhesiveness and elasticity can be obtained.

As the aliphatic (meth) acrylate-based monomer, an acrylate monomer is more preferable than a methacrylate monomer, and a molded article having excellent softness is easily obtained.

Among the aliphatic (meth) acrylate monomers, the aliphatic chain hydrocarbon group in the aliphatic (meth) acrylate monomer having an aliphatic chain hydrocarbon group having 4 or more carbon atoms is not particularly limited. An alkyl group or an alkenyl group having a number of 4 or more is preferable.
The upper limit of the carbon number is not particularly limited, but is preferably 12 or less from the viewpoint of excellent compatibility with the oligomer. Particularly preferred is an alkyl group having 4 to 12 carbon atoms.
Specific examples of the aliphatic (meth) acrylate monomer having an aliphatic chain hydrocarbon group having 4 or more carbon atoms include alkyl (such as n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate). Meth) acrylate; alkenyl (meth) acrylates such as 2-butenyl (meth) acrylate and 4-pentenyl (meth) acrylate. Among these, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable.

As the aliphatic cyclic structure in the aliphatic (meth) acrylate monomer having an aliphatic cyclic structure, for example, a cyclohexyl structure, an isobornyl structure, a dicyclopentanyl structure, an adamantyl structure, and the like are preferable. Thereby, it can be made more excellent in light resistance and heat resistance. Among these, more preferred are a cyclohexyl structure and an isobornyl structure.

Specific examples of the aliphatic (meth) acrylate monomer having the aliphatic cyclic structure include, for example, cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, and the like. (Meth) acrylate having a cyclohexyl structure; (meth) acrylate having an isobornyl structure such as isobornyl (meth) acrylate and isobornyl di (meth) acrylate; having an adamantyl structure such as adamantyl (meth) acrylate and adamantyl di (meth) acrylate ( (Meth) acrylate; dicyclopentanyl (meth) acrylate, dicyclopentanyl di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (Meth) acrylate, tricyclodecane methanol (meth) acrylate, tricyclodecane dimethanol (meth) acrylate. Among these, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate are preferable. More preferred are cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate.

Specific examples of the aliphatic (meth) acrylate monomer having a heterocyclic structure include, for example, PT810 manufactured by Ciba Specialty Chemicals; ERL4234, 4299, 4221, 4206 manufactured by UCC; FA- manufactured by Hitachi Chemical Co., Ltd. 731A (a compound having a triazine ring; tris (2-acryloyloxyethyl) isocyanurate).

Specific examples of the aliphatic (meth) acrylate monomer having a neopentyl structure and the aliphatic (meth) acrylate monomer having a neopentyl structure and an alkylene glycol structure include, for example, neopentyl (meth) acrylate and neopentyl di (meth) acrylate. , Neopentyl glycol (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, and the like. Among these, neopentyl glycol di (meth) acrylate and ethoxylated neopentyl glycol di (meth) acrylate are preferable. More preferred is neopentyl glycol di (meth) acrylate.

Specific examples of the aliphatic (meth) acrylate monomer having an alkylene glycol structure include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,12-dodecanediol, neopentyl glycol, ethoxylated neopentyl glycol, propoxylated neopentyl glycol and other alkylene glycols, diols Examples include (meth) acrylate and di (meth) acrylate. More specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene Glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butane Examples include diol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,12-dodecanediol di (meth) acrylate.

Among these, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol glycol (meth) acrylate and di (meth) acrylate are preferable. If the alkylene glycol chain is too long, the hygroscopicity of the resulting molded product may not be sufficiently reduced. If the alkylene glycol chain is too short, the resulting molded product may not have sufficient elasticity. . More preferred are di (meth) acrylates of any of these glycols. Specific examples of such di (meth) acrylates of glycol include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and propylene glycol di (meth). Preferred are acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate and the like. More preferred are diethylene glycol di (meth) acrylate and dipropylene glycol di (meth) acrylate. Among these, more preferred are diacrylates of any of these glycols. Acrylate is more preferable than methacrylate because it has a higher reactivity and is easy to obtain a molded article having excellent flexibility.
Of the aliphatic (meth) acrylate monomers having an alkylene glycol structure, those having a repeating structure of an oxyalkylene chain and having a weight average molecular weight of 1000 or more are structurally aliphatic (meth). This also applies to acrylate oligomers.

The aliphatic (meth) acrylate monomer having a (meth) acryloyl group and other polar group in one molecule is one (meth) acryloyl group and one or more other polar groups in the structure. It only has to have. When the monomer has two or more other polar groups, the other polar groups may be the same or different from each other.
The other polar group is not particularly limited as long as it is a polar group (bond), but is preferably a polar group having an oxygen atom. Examples of the polar group having an oxygen atom include a hydroxyl group, a urethane group (bond), an ester group (bond), an ether group (bond), a carbonate group (bond), and a functional group having these polar groups. It is done. Among these, a hydroxyl group and a functional group having a hydroxyl group are preferable. More preferred is a hydrocarbon group having a hydroxyl group, and particularly preferred is a hydroxyalkyl group having 1 to 3 carbon atoms.
Note that a polar group containing a (meth) acryloyl group in the structure, such as a (meth) acryloxyalkyl group, is also included in the other polar groups.
In addition, the aliphatic (meth) acrylate monomer having a heterocyclic structure described above and the aliphatic (meth) acrylate monomer having an alkylene glycol structure also have a (meth) acryloyl group and another polar group in one molecule. It corresponds to the aliphatic (meth) acrylate monomer which it has.

Preferable specific examples of the aliphatic (meth) acrylate monomer having a polar group other than the (meth) acryloyl group include 2-hydroxyethyl acrylate, hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2- (2-ethoxyethoxy) ) Ethyl acrylate (ethyl carbitol acrylate), caprolactone acrylate, neopentyl glycol diacrylate, ethoxylated (9) trimethylolpropane triacrylate, and the like. Among these, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, and ethyl carbitol acrylate.

The composition ratio (aliphatic (meth) acrylate oligomer / aliphatic (meth) acrylate monomer) of the aliphatic (meth) acrylate oligomer and the aliphatic (meth) acrylate monomer for forming the molded article is as follows: The mass ratio is preferably 30/70 to 99/1. When the composition ratio between the oligomer and the monomer is within the above range, a molded article having excellent adhesiveness can be easily produced. The composition ratio is more preferably 50/50 to 95/5, and still more preferably 60/40 to 90/10.

<Resin composition for molded body>
The molded article of the present invention is formed of a molded resin composition (hereinafter also simply referred to as a resin composition) containing an aliphatic (meth) acrylate oligomer and an aliphatic (meth) acrylate monomer as essential components. It is preferred that The aliphatic (meth) acrylate oligomer and the aliphatic (meth) acrylate monomer, and preferred modes and mass ratios thereof are the same as those described above. Such a resin composition for molded bodies containing the aliphatic (meth) acrylate oligomer and the aliphatic (meth) acrylate monomer as essential components is also one aspect of the present invention.
More preferably, it is comprised by the resin composition for molded objects containing an aliphatic (meth) acrylate type oligomer, an aliphatic (meth) acrylate type monomer, and a polymerization initiator.
The said resin composition may contain other components other than an aliphatic (meth) acrylate type oligomer, an aliphatic (meth) acrylate type monomer, and a polymerization initiator, and these components are 1 type (s) or 2 or more types. Can be used.

The resin composition contains an aliphatic (meth) acrylate oligomer and an aliphatic (meth) acrylate monomer as essential polymerization components, but may further contain other polymerization components or polymer components.
In order for the molded article of the present invention to have excellent characteristics such as adhesiveness, softness, and light transmittance, the proportion of the polymerization essential component contained in the resin composition is such that the polymerization essential component, other polymerization component And it is preferable that it is 80 mass% or more with respect to 100 mass% of total amounts of a polymer component. More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more, Most preferably, it is 99 mass% or more.
Examples of the other polymerization component include aliphatic (meth) acrylate oligomers having a weight average molecular weight of less than 1000 and vinyl monomers other than aliphatic (meth) acrylate monomers.
As the vinyl monomer other than the aliphatic (meth) acrylate monomer, for example, a (meth) acrylate monomer having an aromatic cyclic structure can be used, but the content thereof is the total amount of essential polymerization components as described later. It is preferable to contain in the range from which the mass ratio of an aromatic ring will be 20 mass% or less with respect to 100 mass%. More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less, Even more preferably, it is 1 mass% or less, Most preferably, it is 0 mass%, ie, it has an aromatic cyclic structure. It does not contain an aliphatic (meth) acrylate monomer.
Examples of the polymer component include polymers of aliphatic (meth) acrylate monomers, rubber components such as polyisoprene and polybutadiene, and silicon rubber.

The resin composition may contain an oligomer or monomer having an aromatic cyclic structure as long as the light resistance and heat resistance of the molded article are not impaired. Group (meth) acrylate-based oligomer and aliphatic (meth) acrylate-based monomer) and the above other polymerization components are preferably included in a range where the mass ratio of the aromatic ring is 20 mass% or less with respect to 100 mass% in total. . More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less, Even more preferably, it is 1 mass% or less, Most preferably, it is 0 mass%, ie, it has an aromatic cyclic structure. It does not contain oligomers and monomers.

Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, acid anhydrides, amines, phenol resins, and the like, and one or more can be used. Among these, it is preferable to use a radical polymerization initiator.

What is necessary is just to select suitably content of the said polymerization initiator by a polymerization system, the polymerization initiator and oligomer to be used, the kind of monomer, etc.
For example, when using a radical polymerization initiator, the content of the radical polymerization initiator is 0.01 to 10 weights with respect to 100 parts by weight of the total amount of the aliphatic (meth) acrylate oligomer and the aliphatic (meth) acrylate monomer. It is preferable to use a part. More preferably, it is 0.1-5 weight part, More preferably, it is 0.2-3 weight part, Most preferably, it is 0.2-2 weight part.

The radical polymerization initiator is not particularly limited as long as it is a compound capable of generating radicals and initiating the polymerization. For example, 1,1′-azobis (cyclohexane-1-carbonitrile), 1,1 '-Azobis-1-cycloheptanenitrile, 1,1'-azobis-1-phenylethane, phenylazotriphenylmethane, 2,2'-azobis- (2-methylbutyronitrile), 2,2'-azo Bisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), methyl 2,2′-azobis-2-methylpropionate, dimethyl 2,2′-azobisisobutyrate, 2,2′azobis Azo initiators such as 2-methylvaleronitrile; benzoyl peroxide, acetyl peroxide, tert-butyl peroxide, propionyl peroxide, lauro peroxide Tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl hydroperoxide, tert-butyl peroxypivalate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, such as t-butylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-amylperisononanoate, t-amylperoxyacetate, t-amylperoxybenzoate, etc. Oxide-based initiators; 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propyl Pan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4 -Methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4 Alkylphenone-based initiators such as -methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,4 Acylphosphine oxide initiators such as 6-trimethylbenzoyl) phenylphosphine oxide; bis (η ⁵ -2,4-cyclopentadiene- 1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium initiators such as titanium; 1,2-octanedione, 1- [4- (phenylthio)- , 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and other oximes Examples thereof include ester initiators.

In addition to the essential components described above, the resin composition can contain a solvent as necessary for the purpose of adjusting the viscosity of the composition. The solvent is not particularly limited and can be used as long as it is a conventionally known organic solvent. However, a solvent that dissolves the above-described aliphatic (meth) acrylate oligomer and aliphatic (meth) acrylate monomer is preferable. For example, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; hydrocarbons such as toluene and xylene; alcohols such as butanol and 2-ethylhexyl alcohol; ethylene glycol, diethylene glycol, (di) ethylene glycol methyl ether, (di) Glycols such as ethylene glycol ethyl ether, (di) ethylene glycol acetate, (di) ethylene glycol diacetate, (di) ethylene glycol methyl ether acetate, propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate And derivatives thereof (ether, ester); esters such as ethyl acetate and butyl acetate are preferred.

The solvent may cause bubbles in the molded body when the resin composition is polymerized to form a molded body, which may cause a decrease in light transmission and transparency. Moreover, if it is used in a large amount, the viscosity of the composition becomes too low, which causes a decrease in the film thickness and shape controllability of the molded body. Therefore, when using a solvent, 30 mass% or less is preferable with respect to 100 mass% of the total amount of the said resin composition, More preferably, it is 15 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 5 mass% or less. More preferably, it is 1% by mass or less. Especially preferably, it is 0.1 mass% or less, Most preferably, it is 0 mass%, ie, it is not using a solvent.

In addition to the above-described components, the resin composition is inorganic fine particles, reactive diluents, saturated compounds having no unsaturated bond, pigments, dyes, antioxidants, as long as the effects of the present invention are not impaired. Adhesion improvers such as ultraviolet absorbers, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization inhibitors, inorganic fillers, organic fillers, and coupling agents , Heat stabilizers, antibacterial / antifungal agents, flame retardants, matting agents, antifoaming agents, leveling agents, wetting / dispersing agents, anti-settling agents, thickeners / anti-sagging agents, anti-coloring agents, emulsifiers, It may contain a slip / scratch prevention agent, an anti-skinning agent, a drying agent, an antifouling agent, an antistatic agent, a conductive agent (electrostatic aid), a photosensitizer and the like.

As a method for curing the resin composition, a normal method can be employed, and for example, it can be performed by heating, irradiation with active energy rays, or the like.
For example, in the case of curing by heating, the curing temperature and curing time may be appropriately set according to the polymerization initiator and the like, for example, preferably 25 to 250 ° C, more preferably 60 to 200 ° C, and still more preferably 80 to 180. ° C, particularly preferably 100 to 180 ° C, most preferably 110 to 150 ° C. The curing time is, for example, when the radical polymerization initiator is used as a polymerization initiator, that is, when cured by a radical polymerization reaction, since the curing reaction can be sufficiently performed even if the curing time is short, The time is preferably within 20 minutes, more preferably within 15 minutes. Further, it is preferably 10 seconds or longer, more preferably 30 seconds or longer.

The heat curing can also be performed in air and / or under an atmosphere of inert gas such as nitrogen under reduced pressure or under pressure. Further, the curing temperature may be changed stepwise. For example, from the viewpoint of improving productivity, etc., the resin composition is held in the mold at a predetermined temperature and time, and then taken out of the mold and left in an inert gas atmosphere such as air and / or nitrogen for heat treatment. It is also possible to do. Moreover, you may combine hardening by active energy ray irradiation.

In the case of curing by irradiation with active energy rays, any active energy rays may be used as long as they can generate active species such as radicals and cations, for example, ultraviolet rays, visible rays, electron beams, α rays, β rays. Ionizing radiation such as γ-rays, microwaves, high frequencies, infrared rays, laser beams and the like are suitable, and may be appropriately selected in consideration of the absorption wavelength of the compound that generates active species. Among these, ultraviolet rays or visible rays having a wavelength of 180 to 500 nm are preferable because they can be easily handled, and light having wavelengths of 254 nm, 308 nm, 313 nm, and 365 nm is particularly effective for curing.
The curing by irradiation with active energy rays can be performed in air and / or in an inert gas, under any atmosphere under reduced pressure or under pressure.

Examples of the light generation source of ultraviolet light or visible light having a wavelength of 180 to 500 nm include, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, an excimer lamp, Short arc lamps, helium / cadmium lasers, argon lasers, excimer lasers, sunlight and the like are suitable. In addition to these light sources, thermal energy may be applied using infrared rays, far infrared rays, hot air, high-frequency heating, or the like.

In the case of curing using an electron beam, the lower limit of the acceleration voltage is set to 10 kV or higher, preferably 20 kV or higher, more preferably 30 kV or higher, and the upper limit is set to 500 kV or lower, preferably 300 kV or lower, more preferably 200 kV or lower. It is mentioned to use the set electron beam. In addition, the lower limit of the electron beam irradiation dose is set to 2 kGy or more, preferably 3 kGy or more, more preferably 5 kGy or more, and the upper limit is set to 500 kGy or less, preferably 300 kGy or less, more preferably 200 kGy or less. . Furthermore, you may provide a thermal energy simultaneously using the said electron beam using infrared rays, far infrared rays, a hot air, high frequency heating, etc.

What is necessary is just to set suitably the irradiation time of the said active energy ray irradiation, ie, the hardening time in hardening by an active energy ray, according to the kind, irradiation amount, etc. of an active energy ray. For example, the irradiation time of ultraviolet rays or visible rays having a wavelength of 180 to 500 nm is preferably 0.1 microseconds to 30 minutes, and more preferably 0.1 milliseconds to 1 minute.

<Molded body>
As a method for producing the molded article of the present invention, the resin composition is applied onto a substrate and polymerized (cured), and then the cured product is peeled off from the substrate. Examples thereof include a method (mold molding method) of releasing a cured product after casting into a mold and curing. Among these, it is preferable to employ a forming method by coating in that the formed body can be easily formed into a sheet shape which is a preferable shape. Specifically, a method in which the resin composition is applied to a polymer film such as PET and polymerized is suitable.

The molded body may contain a structure derived from an oligomer or monomer having an aromatic cyclic structure within a range that does not impair light resistance and heat resistance, but the content thereof is based on the total amount of the molded body of 100% by mass. The range which becomes 20 mass% or less by the mass ratio of an aromatic ring is preferable. More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less, Even more preferably, it is 1 mass% or less, Most preferably, it is 0 mass%, ie, it has an aromatic cyclic structure. An aromatic cyclic structure derived from an oligomer and a monomer is not included.

The shape of the molded body is preferably a sheet shape. Specifically, the thickness of the molded body is preferably 100 μm or more and 2000 μm or less. The lower limit of the thickness of the molded body is more preferably 200 μm, still more preferably 300 μm, and most preferably 400 μm. Moreover, as an upper limit of the thickness of a molded object, More preferably, it is 1500 micrometers, More preferably, it is 1000 micrometers. When the molded body has such a thickness, it can be interposed without any gaps in the voids present inside the optical apparatus or the like.

The molded body is preferably an elastic body. Specifically, the storage elastic modulus at 20 ° C. of the molded body is preferably 0.1 to 30 MPa. More preferably, it is 0.5-20 MPa, More preferably, it is 1-10 MPa.
The storage elastic modulus can be measured by a dynamic viscoelasticity measuring device (RSA-III, manufactured by T.A. Instruments Inc.). Usually, it measures in the temperature range of -20 degreeC-100 degreeC. In the present invention, the storage elastic modulus at 20 ° C. is adopted.
The hardness of the molded body can also be evaluated by Shore hardness. In this case, the Shore A hardness is preferably 70 or less. More preferably, it is 60 or less, More preferably, it is 50 or less. The Shore A hardness of the molded body is preferably 10 or more. More preferably, it is 15 or more. When the Shore A hardness is in the above range, the molded product has excellent impact absorption, and particularly exhibits excellent durability in optical transmission applications. The Shore A hardness is a value measured in an air atmosphere maintained at a constant temperature of 23 ° C.
The Shore A hardness can be confirmed by measuring the hardness after 15 seconds using an A-type durometer (rubber hardness meter, manufactured by Asker) based on JISK 6253. The sample shape is 100 mm wide x 20 mm deep x 6 mm thick.

Moreover, it is preferable that the said molded object is what has adhesiveness. Specifically, when the adhesiveness is evaluated by Shore hardness, it is preferable that the Shore A hardness at 23 ° C. of the molded body is 70 or less. More preferably, it is 60 or less, More preferably, it is 50 or less. The Shore A hardness of the molded body is also preferably 5 or more. More preferably, it is 10 or more. When the Shore A hardness is in the above range, since the molded body has appropriate tackiness, the molded body is brought into close contact with the adherend without causing voids even if the adherend surface is uneven. Can do.
Moreover, it is preferable that the said molded object is 5 g / 25mm or more in adhesive force. More preferably, it is 10 g / 25 mm or more, More preferably, it is 20 g / 25 mm or more. The adhesive strength of the molded body is also preferably 500 g / 25 mm or less. More preferably, it is 400 g / 25 mm or less, More preferably, it is 300 g / 25 mm or less. Adhesive strength is 25 mm wide PET film (thickness 25 μm) attached to the molded body sheet in an air atmosphere kept at a constant temperature of 23 ° C., and 1 reciprocating with a 2 Kg roller. It can be measured as the adhesive strength when peeled in the 180 ° direction at a peel rate of / min.

Further, the molded body preferably has a visible light transmittance of 80% or more. Specifically, the parallel line transmittance at 400 nm is preferably 80% or more. As a result, it is possible to achieve high light transparency and transparency that are required particularly in applications to optical transmission bodies. The parallel line transmittance at 400 nm is more preferably 85% or more, and still more preferably 90% or more.
The transmittance can be measured using a sample having a thickness of 1 mm using a UV-VIS spectrophotometer (Agilent 8453, manufactured by Agilent Technologies).

Moreover, it is preferable that the said molded object is refractive index 1.40-1.60. When the refractive index is in such a range, the molded body is made of acrylic resin (plate) or glass used for a protective part of a display device, glass used for a light source lamp, acrylic resin used for a light guide plate ( Plate), polycarbonate resin (plate), and the like, and thus has high refractive index. More preferably, it is 1.45 to 1.55 as a refractive index of the said molded object, More preferably, it is 1.47 to 1.53.
The refractive index can be measured using a refractometer (Atago Co., Ltd., DR-M2).

Moreover, it is preferable that the said molded object is what has heat resistance. Specifically, it is preferable that the parallel line transmittance at 400 nm of the molded article after the heat resistance test, that is, after being held in an 85 ° C. heating furnace (atmosphere: air) for 1000 hours, is 75% or more. More preferably, it is 80% or more, More preferably, it is 85% or more.

Moreover, it is preferable that the said molded object is what has light resistance. Specifically, after the light resistance test, that is, after forming the molded body on a metering weather meter (Suga Test Instruments Co., Ltd., M6T, 100 mW / cm ² ) and performing a 100-hour accelerated light resistance test, The parallel line transmittance at 400 nm of the body is preferably 75% or more. More preferably, it is 80% or more, More preferably, it is 85% or more.

When the molded body is a sheet, the molded body sheet is a laminated sheet in which the layer formed of the molded body sheet of the present invention is essential, in addition to the form in which the molded body is a single layer structure sheet having a homogeneous composition. The form is also included in the molded article of the present invention.
The configuration of the laminated sheet is a sheet having a laminated structure composed of two layers having different compositions within the range of the composition of the molded body of the present invention (laminated sheet: form (i)), or of the present invention. The case where it is a sheet | seat (laminated sheet: form (ii)) which has a laminated structure of the layer which consists of a molded object, and a layer different from the molded object of this invention is illustrated as a preferable form.
In the laminated sheet, at least one layer is preferably a soft layer having a Shore A hardness of 70 or less.
Form (i) is a laminate in which two or more molded articles of the present invention are laminated, but the combination is not particularly limited.
For example, when the molded body (laminated sheet) is used as a bonding material for an optical transmission medium, the materials and refractive indexes of two bonded materials to be bonded are usually different. For example, a combination of glass and resin, a combination of acrylic resin and silicone resin, a combination of polycarbonate resin and silicone resin, or the like. Therefore, the laminated sheet is composed of two layers or three or more layers, and the refractive index of the molded body forming each layer is changed stepwise within the range of the refractive index of the two connected materials, or the material of the connected material is In addition, it is a preferable embodiment that the two outermost layers have different polarities (hydrophilicity and hydrophobicity) and adhesive strength. By using the laminated sheet in such a form, connection with high light transmission efficiency can be achieved. The characteristics in each of these layers can be controlled by adjusting the composition of the composition for forming the layer. Specifically, the blending ratio of the aliphatic (meth) acrylate oligomer and the aliphatic (meth) acrylate monomer, which are essential polymerization components, and the molecular weight of the aliphatic (meth) acrylate oligomer are different. Moreover, it can control by mix | blending the monomer and oligomer component which have the aromatic ring mentioned above in the range which does not impair the characteristic of a molded object as needed.

In addition, the molded body of the present invention usually needs to be cut into a desired shape when it is used after being produced. In particular, when used as a bonding material for an optical transmission medium, high processing accuracy is required. Moreover, high arrangement | positioning precision which affixes the molded object cut and processed into the desired shape to the desired position of a to-be-connected material with high precision is requested | required. In order to make the molded body excellent in these cutting processing accuracy and placement accuracy, use an aliphatic (meth) acrylate oligomer having a low weight average molecular weight as an essential component of polymerization for forming the molded body. Is preferred. Specifically, it is preferable to use an aliphatic (meth) acrylate oligomer having a weight average molecular weight of less than 5000. Furthermore, it is preferable to use those having a weight average molecular weight of less than 4000. Further, in the total amount of 100% by mass of the aliphatic (meth) acrylate oligomer, the proportion of the aliphatic (meth) acrylate oligomer having a weight average molecular weight of less than 5000 is preferably 50% by mass or more, more preferably 80%. It is at least mass%, particularly preferably 100 mass%. Moreover, it is preferable that the ratio of the aliphatic (meth) acrylate oligomer having a weight average molecular weight of less than 5000 is 50% by mass or more with respect to 100% by mass of the polymerization essential component.
However, as described above, different properties such as the refractive index, adhesive strength, surface polarity, etc. of the molded product due to different compositions make it excellent in cutting processing accuracy and placement accuracy, but for optical transmission media. In order to obtain a molded body (sheet) excellent in various properties as a connecting material, it is preferable to use a laminated sheet. That is, at least one layer is a layered sheet having a configuration in which the above-described layer is excellent in cutting accuracy and arrangement accuracy, and one or more other layers are formed of a composition having desired characteristics. preferable. Furthermore, it is preferable to use a laminated sheet that essentially includes the above-described layer (also referred to as a layer (A)) excellent in cutting processing accuracy and arrangement accuracy and a layer (also referred to as a layer (B)) excellent in adhesive strength. .
In this case, the layer (A) is a layer formed using an aliphatic (meth) acrylate oligomer for forming the layer having a weight average molecular weight of less than 5000, and the preferred embodiment is as described above.
On the other hand, the layer (B) is preferably a layer formed using an aliphatic (meth) acrylate oligomer for forming the layer having a weight average molecular weight of 5000 or more. More preferably, the aliphatic (meth) acrylate oligomer has a weight average molecular weight of 6000 or more, and more preferably a weight average molecular weight of 8000 or more. Moreover, it is preferable that the ratio of the aliphatic (meth) acrylate oligomer having a weight average molecular weight of 5000 or more in the total amount of 100 mass% of the aliphatic (meth) acrylate oligomer is 50 mass% or more, more preferably 80%. It is at least mass%, particularly preferably 100 mass%. Moreover, it is preferable that the ratio of the aliphatic (meth) acrylate oligomer having a weight average molecular weight of 5000 or more is 50% or more with respect to 100% by mass of the polymerization essential component.

The laminated sheet of the above-described form (i) is prepared by preparing two types of molded bodies having different compositions of the present invention and laminating them by extrusion molding or the like, or the sheet (1) which is the molded body of the present invention. Two or more layers are formed by applying, curing, or cast polymerization a resin composition different from the resin composition for forming the sheet (1), which is the composition for a molded body of the present invention, on the surface of The thing made into the laminated structure which consists of is illustrated. Therefore, the laminated sheet of the form (i) can be formed from the resin composition for molded bodies of the present invention.
The thickness of the laminated sheet is preferably in the same range as described as the preferred thickness when the molded article of the present invention is formed into a sheet. Moreover, it is preferable that the thickness of each layer which comprises a laminated sheet is the range of 100-1000 micrometers normally.

In the case of the above-mentioned form (ii), the layer having a composition different from that of the molded product of the present invention (also referred to as a heterogeneous layer) is not particularly limited in composition, physical properties, etc. It is preferable that the refractive index, the polarity, the adhesive force, and the like are different from those of the layer made of the molded body, and it is particularly preferable that the layer has excellent cutting processing accuracy and placement accuracy. As a layer excellent in cutting processing accuracy and arrangement accuracy, for example, a conventionally known thermoplastic resin film, (meth) acrylic polymer film and the like are preferable.
Among the thermoplastic resin films, polyester resins such as PET and PEN; polyolefin resins such as polyethylene, polypropylene, and polycycloolefin; polycarbonate resins; polyimide resins; PFA (perfluoroalkoxy fluororesin), FEP (ethylene tetrafluoride, hexa Fluorine resins such as fluorinated propylene copolymer resin) and ETFE (ethylene / chlorotrifluoroethylene copolymer resin) are preferable. In particular, polyester resin, polyolefin resin, polycarbonate resin, and polyimide resin are adhesive to the molded body layer. It is preferable because of its excellent resistance. Further, those subjected to hydrophilic treatment such as corona treatment and plasma treatment are preferable in terms of excellent adhesion to a layer made of a molded body. A laminated sheet having a thermoplastic resin film as a heterogeneous layer can be produced by, for example, applying and polymerizing the molded resin composition of the present invention to a thermoplastic resin film.
The (meth) acrylic polymer film is at least one polymer selected from the group consisting of the above-mentioned aliphatic (meth) acrylate monomers and aliphatic (meth) acrylate oligomers having a weight average molecular weight of less than 1000. A (co) polymer film obtained by (co) polymerizing a polymerizable composition containing components is preferred. Furthermore, in order to obtain a molded article having excellent cutting properties, it is preferable to use a polyfunctional polymerization component as the monomer or oligomer, and the ratio of the polyfunctional polymerization component is 5% by mass with respect to 100% by mass of the total polymerization component. The above is preferable. Moreover, the polymerization shrinkage at the time of forming the (meth) acrylic polymer film on the molded body layer is suppressed, and it is easy to obtain a material having excellent adhesion at the interface with the molded body layer. On the other hand, it is preferable to make the said oligomer into 50 mass% or more. The laminated sheet having a (meth) acrylic polymer film as a heterogeneous layer is, for example, a method of coating and polymerizing the polymerizable composition on the molded sheet of the present invention, and the molded product of the present invention on a (meth) acrylic polymer film. It can manufacture by the method etc. which apply | coat and polymerize the resin composition for water.
In the case of the above form (ii), the thickness of the layer formed of the molded article of the present invention is preferably within the same range as described as the preferred thickness when the molded article of the present invention is formed into a sheet shape. The thickness of the heterogeneous layer is preferably in the range of 100 to 1000 μm.

When the molded body is a sheet, the molded body is used in the state of the single layer structure or the laminated structure described above, for example, as a bonding layer constituting an optical transmission medium, but at least one surface is an adhesive elastic body Therefore, it is preferable that one side or both sides of the molded body be protected by a polymer film as a form to be used for joining because of excellent handleability.
As a protective film, it selects suitably according to the magnitude | size of the adhesive force of the molded object surface. Usually, a surface having a high adhesive strength of 5 g / 25 mm or more (also referred to as a highly adhesive surface) is not subjected to a release-treated polymer film or in particular a release treatment or an adhesive treatment. A polymer film (also referred to as an untreated film) is preferably used.
Preferable specific examples of the polymer film subjected to the release treatment include release-treated PET films such as Panapeel TP series (manufactured by Panac Co., Ltd.), Unipeel TR series (manufactured by Unitika Ltd.), and the like.
Specific examples of the untreated film include PET such as Lumirror T60, Lumirror S10 (manufactured by Toray Industries, Inc.), Teijin Tetron G2 and O3 (manufactured by Teijin DuPont Films), polyester such as PEN, polyethylene, polypropylene, and polycarbonate. Polymer films of fluororesins such as PFA (perfluoroalkoxy fluororesin), FEP (tetrafluoroethylene / hexafluoropropylene copolymer resin), ETFE (ethylene / chlorotrifluoroethylene copolymer resin) It is done. Among these, a polyester film is preferable, and a PET film is most preferable.
The thickness of the polymer film is not particularly limited, but is preferably 50 μm or more from the viewpoint that it is easy to control when it is cut in a later operation, particularly when processed in a half cut state. More preferably, it is 75 micrometers or more, More preferably, it is 100 micrometers or more. On the other hand, the upper limit is preferably 1000 μm or less and more preferably 500 μm or less from the viewpoint of excellent handleability.

On the other hand, as a protective film used for a surface having a low adhesive strength of less than 5 g / 25 mm (also referred to as a low adhesive surface), an adhesive layer is formed on the surface of the base film on the side in contact with the low adhesive surface. A polymer film (also referred to as an adhesion-treated film) having s is preferable.
As the base film, for example, polyethylene, polypropylene, polycarbonate, polyester and the like are preferable, among which polyester is preferable, and PET is particularly preferable.
As the adhesive layer, a self-adhesive layer (elastomer layer) and an acrylic adhesive layer are preferable, and an acrylic adhesive layer is more preferable.
Preferred examples of the polymer film having a self-adhesive layer include self-adhesive PET films such as Gel Poly series (manufactured by Panac Co., Ltd.) and CPETT series (manufactured by Oji Tac Co., Ltd.). Examples of polymer films having an acrylic adhesive layer include PET such as re-peeling film NT series, GN series, GS series (manufactured by Panac), heat-resistant re-peeling film CT series, HT series, ST series (manufactured by Panac). A film is preferably exemplified.
Although it does not specifically limit as thickness of an adhesion processing film, From the point which is easy to cut, 50 micrometers or more are preferable. More preferably, it is 75 μm or more. On the other hand, the upper limit is preferably 1000 μm or less, more preferably 500 μm or less, and particularly preferably 200 μm or less from the viewpoint of excellent handleability.

When the molded body sheet is the above-mentioned laminated molded body, the above-mentioned release treatment film or untreated film is laminated as a protective film on the high-adhesion surface side, and on the low-adhesion surface side, The form formed by arranging an adhesive treatment film is preferred. When it is such a form, it is preferable that the adhesive force in the adhesive treatment film of the low adhesive surface side is lower than the adhesive force which the high adhesive layer in a laminated molded body has. By doing in this way, when peeling a protective film, delamination and delamination in a laminated molded object can be suppressed.

Although the manufacturing method of the molded object sheet which provided the protective film is not restrict | limited in particular, For example, after apply | coating and hardening the resin composition for molded objects of this invention on the surface of a 1st protective film, the 1st protection After forming a molded body sheet by a method such as laminating the second protective film on the non-contact surface side of the film or by casting polymerization from the molded resin composition of the present invention, both surfaces are protected films The method of making it adhere | attach by performing the lamination process in the state pinched | interposed is illustrated. Although the above-mentioned curing is preferably both thermal curing and photocuring, photocuring is preferable from the viewpoint of excellent film thickness controllability. As light curing, ultraviolet curing is preferable.
Further, when the molded body sheet is a laminated molded body, a sheet whose surface is protected with a protective film can be produced in the same manner, but a particularly preferable production method including the production of a laminated molded body composed of layers having different adhesive forces is also possible. For example, the following method is adopted.
Step 1) Resin composition for molded body for forming a highly adhesive layer, preferably a highly adhesive layer, on the surface of the first protective film (in the case of a release-treated film, the surface subjected to a release treatment) Is applied and cured to form a soft elastic layer composed of a highly adhesive layer on the surface of the first protective film.
Step 2) Laminating on the surface of the first protective film by applying and curing a composition having a lower adhesive strength than the layer, preferably a low-adhesive layer, on the surface of the soft elastic layer. A molded body layer is formed.
Step 3) Lamination treatment is performed in a state where the second protective film is laminated on the surface of the laminated molded body layer (surface having lower adhesiveness).
By the steps 1) to 3), a laminated molded body protected by the first protective film and the second protective film can be produced.
As a 1st protective film in the above-mentioned process 1), a mold release process or an untreated film is preferable, and as a 2nd protective film in the above-mentioned process 3), an adhesion processing film is preferable. The curing in the steps 1) and 2) is preferably both thermal curing and photocuring, but photocuring is preferable from the viewpoint of excellent film thickness controllability, and ultraviolet curing is preferable as photocuring.
Even when the molded body sheet is a laminated sheet having a layer excellent in the above-described cutting processability and arrangement characteristics, it is more excellent in cutting processability and arrangement characteristics by adopting a configuration in which a protective film is arranged on one side or both sides. Therefore, it is preferable. As described above, the type of protective film to be used is preferably selected according to the magnitude of the adhesive strength of each layer.
In addition, in both cases where the molded body has a single layer structure and a laminated structure, the form in which both surfaces of the molded body are protected by the protective film has been described, but the present invention is not limited to these forms. For example, a form in which the protective film is disposed only on one surface of the molded body is one of the preferred embodiments of the present invention. In the form in which the protective film is disposed only on one side of the molded body, when the molded body is the laminated molded body described above, a form in which the protective film is disposed only on the highly adhesive layer is preferable.

Furthermore, it is preferable that the molded body of the present invention is cut into a width, length, and shape necessary for use. Preferred examples of the cutting method include laser cutting, Thomson punching, slitting, and shearing.
The molded body or the molded body provided with the protective film may be cut into the required size and shape together with the protective film, but the following forms are preferred. That is, at least one surface of a molded body cut into a required size and shape has a protective film larger than the molded body (a protective film that can completely cover the surface of the molded body and has an excess portion). It is preferable that the film is in the form of a film. In such a form, the protective film not only protects the surface of the molded body, but also has a function as a support for supporting the molded body. When the molded body is supplied in such a form and used as a bonding material, for example, the adherend medium can be bonded efficiently with high positional accuracy.
Furthermore, the protective film as the support is preferably in a half-cut state. The half-cut state refers to a state in which a protective film larger than the molded body is cut by a part of the length in the thickness direction in accordance with the size and shape of the molded body. In the protective film in such a state, the surplus portion when the surface of the molded body is covered is not completely cut, so that the function as a support is maintained. By setting it as such a form, a protective film can be easily peeled from a molded object at the time of use.
In a more preferable form, protective films are arranged on both sides of the molded body, one protective film and the molded body are cut into a desired size and shape, and the other protective film is not cut or half-cut. It is the form which is a state made, ie, a state having a function as a support. Particularly preferred is a form in which the other protective film is half cut.
Moreover, when a protective film is arranged on both surfaces of a molded body, and one protective film is a release-treated film or an untreated film, and the other protective film is an adhesive-treated film, an adhesive-treated film Is cut into the same shape and size as the molded body, and the release-treated film or untreated film preferably has a function as a support. Such a form is preferably employed when the molded body is a laminated molded body. In the case of cutting, it is preferable to perform cutting from the adhesive-treated film side. A structure in which a molded body is cut into a desired size and shape together with a protective film (adhesive film) on a half-cut protective film (release or non-treated film) by cutting in this way. A sheet in which a plurality of laminates are supported and fixed is obtained.

<Use of molded body>
Since the molded article of the present invention has high light transmittance and transparency, it can be suitably applied to optical applications. In addition, the molded body has appropriate elasticity and adhesiveness, has excellent adhesion to the adherend, and is also excellent in durability, and thus exists in an optical device such as a display device, for example. It can also be used as a member interposed in the gap. In particular, the present invention is preferably applied to a light transmission body (light transmission adhesive sheet) interposed in a gap existing between a light source of a backlight such as a liquid crystal display and a light guide plate or between a display panel and a protective panel. . Such an optical transmission body is required to be able to adhere to the adherend surface without generating a gap between the optical adherend and to be excellent in transparency and difficult to deteriorate in the use environment. Since the molded article of the present invention is excellent in adhesiveness, transparency, and durability, it can exhibit high performance as the above-described optical transmission body. Thus, it is one of the preferred embodiments of the present invention that the molded body is a molded body for an optical transmission body.

Since the molded body of the present invention has the above-described configuration, it has appropriate elasticity and adhesiveness, is excellent in transparency and durability, and can sufficiently suppress a decrease in light transmission properties. And such a molded object can be used suitably as members, such as a light transmission adhesive sheet interposed in the space | gap etc. which exist in optical apparatuses, such as a display apparatus.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “% by mass”.

<Synthesis of aliphatic (meth) acrylate oligomer (hereinafter also referred to as component A)>
Synthesis example 1
In a reactor equipped with a thermometer, a condenser, a nitrogen gas inlet tube and a stirrer, 208.6 parts of 2-ethylhexyl acrylate, 1.4 parts of 2-hydroxyethyl methacrylate, 0.21 n-dodecyl mercaptan as a chain transfer agent Then, 280.6 parts of ethyl acetate was charged as a solvent, and the reactor was replaced with nitrogen gas. Next, the internal temperature was raised to 85 ° C. while stirring the above mixture, and then 2,2′-azobis- (2-methylbutyronitrile) (trade name “ABN-E”; Japan as a polymerization initiator The reaction was started by adding 0.175 parts (made by Hydrazine Kogyo Co., Ltd.) and 3.15 parts ethyl acetate as a solvent. 10 minutes after the start of polymerization, a mixture of 486.8 parts of 2-ethylhexyl acrylate, 3.2 parts of 2-hydroxyethyl methacrylate and 0.49 parts of n-dodecyl mercaptan as a chain transfer agent was added dropwise over 60 minutes from the dropping funnel. . Further, 0.175 part of ABN-E as a polymerization initiator and 14 parts of ethyl acetate as a solvent were similarly dropped from another dropping funnel. After completion of dropping, the dropping funnel was washed with 119 parts of ethyl acetate and added to the reactor. Then, after making it react at reflux temperature for 5 hours, it diluted with 105 parts of ethyl acetate, and obtained the solution of the acrylic polymer of 54% of non volatile matter density | concentration.
In a reactor equipped with a thermometer, a cooler, a nitrogen gas inlet tube and a stirrer, 100 parts of the above acrylic polymer solution in terms of solid content and 2,2′-methylenebis (4-methyl-6 as a polymerization inhibitor) -T-butylphenol) (trade name “ANTAGE W-400”; manufactured by Kawaguchi Chemical Co., Ltd.) 0.06 parts, 2-acryloyloxyethyl isocyanate (trade name “Karenz AOI”; manufactured by Showa Denko KK) 0.36 parts In addition, stirring was performed while bubbling a mixed gas of nitrogen / air = 2/1, and the internal temperature was raised to 70 ° C. Thereafter, 0.04 part of dibutyltin dilaurate was added as a catalyst and reacted at 70 ° C. for 3 hours, and then the disappearance of the 2273 cm ⁻¹ peak derived from the isocyanate group was confirmed by FT-IR analysis. The temperature was raised to 80 ° C., and the solvent was removed while stirring at 10 Torr for 3 hours to obtain an oligomer (a).

Synthesis example 2
A reactor equipped with a thermometer, a cooler, a nitrogen gas inlet tube and a stirrer was charged with 57 parts of ethyl carbitol acrylate, 3 parts of acrylic acid, and 420 parts of toluene as a solvent, and then the reactor was replaced with nitrogen gas. . Next, the internal temperature was raised to 85 ° C. while stirring the above mixture, and then 2,2′-azobis- (2-methylbutyronitrile) (trade name “ABN-E”; Japan as a polymerization initiator 2.4 parts of Hydrazine Kogyo) and 24 parts of toluene as a solvent were added to initiate the reaction. Ten minutes after the start of polymerization, a mixture of 513 parts of ethyl carbitol acrylate, 27 parts of acrylic acid, 3.6 parts of ABN-E as a polymerization initiator, and 48 parts of toluene as a solvent was added dropwise over 90 minutes from the dropping funnel. Further, 3 parts of mercaptopropionic acid as a chain transfer agent and 60 parts of toluene as a solvent were similarly dropped from another dropping funnel. After completion of dropping, the dropping funnel was washed with 48 parts of toluene and added to the reactor. After holding at 85 ° C. for 90 minutes, the temperature was raised to 100 ° C. and reacted for 90 minutes, followed by cooling to obtain an acrylic polymer solution having a nonvolatile content concentration of 51%.
In a reactor equipped with a thermometer, a cooler, a gas introduction tube and a stirrer, 335 parts of the acrylic polymer solution in terms of solid content and 2,2′-methylenebis (4-methyl-6--6) as a polymerization inhibitor t-butylphenol) (trade name “ANTAGE W-400”; manufactured by Kawaguchi Chemical Industry Co., Ltd.) 1.66 parts, 11.2 parts of glycidyl methacrylate while stirring by bubbling a mixed gas of nitrogen / air = 2/1 Then, 0.33 part of zinc octenoate was added as a catalyst, reacted at 100 ° C. for 3 hours, then heated to 110 ° C. and further reacted for 6 hours, and the disappearance of glycidyl methacrylate was confirmed by GC analysis. The temperature was raised to 100 ° C., and the solvent was removed while stirring at 10 Torr for 3 hours to obtain an oligomer (b).

<Preparation of resin composition for light transmission adhesive sheet>
Preparation Example 1
Weigh 80 parts of CN9873 (aliphatic urethane acrylate oligomer, manufactured by Sartomer), 20 parts of SR502 (produced by ethoxylated (9) trimethylolpropane triacrylate, manufactured by Sartomer), and 1 part of IRGACURE 184 (produced by Ciba Japan). By mixing, a resin composition (1) was obtained.

Preparation Examples 2-36
Preparation Example 1 except that the A component shown in Tables 1 and 2 and the aliphatic (meth) acrylate monomer (hereinafter also referred to as B component) shown in Tables 1 and 2 were used in the proportions shown in Tables 1 and 2. In the same manner as above, resin compositions (2) to (36) were obtained.

Each compound in Tables 1 and 2 is as follows.
CN9893: manufactured by Sartomer, polyester urethane acrylate CN991: manufactured by Sartomer, polyester urethane acrylate UV-3000B: manufactured by Nippon Gosei Kagaku Co., Ltd., polyester urethane acrylate CN9002: manufactured by Sartomer, polyether urethane acrylate CN9178: manufactured by Sartomer , Polyether urethane acrylate CN966J75: manufactured by Sartomer, polyester urethane acrylate 75% / isobornyl acrylate 25%
CN966H90: manufactured by Sartomer, 90% polyester urethane acrylate / 10% ethoxyethoxyethyl acrylate
CN2271E: Sartomer, polyester acrylate CN2273: Sartomer, polyester acrylate UC-102: Kuraray, methacryloyl group-modified polyisoprene CN9782: Sartomer, polyester urethane acrylate (aromatic)
CN2254: Sartomer, polyester acrylate (aromatic)
CN2270: Polyester acrylate manufactured by Sartomer

BA: butyl acrylate IB-XA: manufactured by Kyoeisha Chemical Co., Ltd., isobornyl acrylate 2EHA: 2-ethylhexyl acrylate HEA: 2-hydroxylethyl acrylate HPA: hydroxylpropyl acrylate SR285: manufactured by Sartomer, tetrahydrofurfuryl acrylate SR256: manufactured by Sartomer , 2- (2-Ethoxyethoxy) ethyl acrylate (also known as ethyl carbitol acrylate)
SR495B: manufactured by Sartomer, caprolactone acrylate NP-A: manufactured by Kyoeisha Chemical Co., Ltd., neopentyl glycol diacrylate SR502: manufactured by Sartomer, triacrylate of trimethylolpropane ethylene oxide 9 mol adduct

<Preparation of light transmission adhesive sheet>
Examples 1, 2, 4, 5, 10, 12 to 15 , 17 to 22, 24 , 26 and 27, Reference Examples 3, 6 to 9, 11, 16, 23 and 25, Comparative Examples 1 to 7
Casting resin compositions (1) to (27) and resin compositions (30) to (36) obtained in Preparation Examples 1 to 27 and Preparation Examples 30 to 36 between two glass plates with a 1 mm spacer. Then, UV irradiation (high-pressure mercury lamp, manufactured by Ushio Electric Co., Ltd., irradiation amount: 500 mJ / cm ² ) was performed to obtain sheets (1) to (27) and sheets (Comparative 1) to (Comparative 7) each having a thickness of 1 mm.

Example 28
The resin composition (28) obtained in Preparation Example 28 was cast between two glass plates with a 0.5 mm spacer, and UV irradiation (high pressure mercury lamp, manufactured by USHIO INC., Irradiation amount 500 mJ / cm ² ) Thus, a soft layer sheet was obtained. Furthermore, the resin composition (29) obtained in Preparation Example 29 was cast with a 0.5 mm spacer, cured under the same conditions, and a layer (a) having a thickness of 0.5 mm and a thickness of 0.5 mm. A sheet (28) having a two-layer structure composed of the layer (b) was obtained.

Example 29 (form which provided the protective film)
The resin composition (22) prepared in Preparation Example 22 was applied to a PET film (Lumirror T60, thickness 100 μm, manufactured by Toray Industries, Inc.), and UV irradiation (high pressure mercury lamp, manufactured by USHIO INC., Irradiation amount 500 mJ / cm ^2). ) To obtain a layer (a) made of the molded product of the present invention having a thickness of 600 μm. Furthermore, by applying and curing the resin composition (29) obtained in Preparation Example 29 under the same conditions, a layer (b) having a thickness of 200 μm was formed on the surface of the layer (a) on the PET film 2 A sheet (29) having a layered molded article layer was obtained.

Example 30 (form which provided the protective film)
The resin composition (27) prepared in Preparation Example 27 was applied to a PET film (Lumirror T60, thickness 100 μm, manufactured by Toray Industries, Inc.), and UV irradiation (high pressure mercury lamp, manufactured by USHIO INC., Irradiation amount 500 mJ / cm ^2). ) To obtain a layer (a) comprising the molded article of the present invention having a thickness of 300 μm. Furthermore, by applying and curing the resin composition (1) obtained in Preparation Example 1 under the same conditions, a layer (b) having a thickness of 600 μm was formed on the surface of the layer (a) on the PET film 2 A sheet (30) on which a layered molded body layer was formed was obtained.

Sheets (29) and (30) had no problem with the peelability of the PET film. That is, although it is a visual judgment, even if the PET film is peeled off from the molded body layer, no attachment of the molded body layer to the peeled PET film is recognized, and the layers (b) and (a) of the molded body layer are not recognized. No delamination was observed.

Examples 1, 2, 4, 5, 10, 12-15 , 17-22 , 24 , 26 and 27-30, Reference Examples 3, 6-9, 11, 16, 23 and 25 and Comparative Examples 1-7 Shore A hardness, storage elastic modulus, refractive index, transparency, heat resistance, light resistance, moisture resistance, adhesion, surface of sheets (1) to (30) and sheets (Comparative 1) to (Comparative 7) obtained Smoothness, handleability (brittleness) and adhesive strength were measured by the methods shown below, and the results are shown in Tables 3-5.
In addition, in storage elastic modulus, transparency, heat resistance, light resistance, moisture resistance, and adhesive strength evaluation, a 1 mm thick sheet obtained by casting between two glass plates with a 1 mm spacer as a sample ( Evaluation sheet) was used. In the sheet | seat which has a multilayer structure obtained in Examples 28-30, what produced the sheet | seat of the above-mentioned thickness 1mm about each layer which comprises a multilayer structure was made into the said sheet | seat for evaluation.

<Shore A hardness>
Based on JISK 6253, the hardness after 15 seconds was measured using an A-type durometer (rubber hardness meter, manufactured by Asker). The sample shape was 100 mm wide x 20 mm deep x 6 mm thick. The measurement was performed in an air atmosphere maintained at a constant temperature of 23 ° C.

<Storage modulus>
The value at 20 ° C. was measured using a dynamic viscoelasticity measuring device (RSA-III, manufactured by TA Instruments Inc.).

<Refractive index>
Measurement was performed using a refractometer (DR-M2 manufactured by Atago Co., Ltd.).

<Transparency>
Using a UV-VIS spectrophotometer (Agilent 8453, manufactured by Agilent Technologies), the parallel line transmittance at 400 nm was measured and evaluated. A film having a parallel line transmittance of 80% or more at 400 nm was evaluated as ◯.

<Heat resistance>
A heat resistance test was conducted for 1000 hours in an 85 ° C. heating furnace (atmosphere: air), the parallel line transmittance at 400 nm of the sheet after the test was measured, and evaluated according to the following criteria.
○: Parallel line transmittance is 80% or more Δ: 75% or more and less than 80% ×: less than 75%

<Light resistance>
The sheet for evaluation was placed in a metering weather meter (Made by Suga Test Instruments Co., Ltd., M6T, 100 mW / cm ² ), and after performing a 100-hour accelerated light resistance test, the parallel line transmittance at 400 nm of the sheet was measured. Evaluation was made according to the following criteria.
○: Parallel line transmittance is 80% or more Δ: 75% or more and less than 80% ×: less than 75%

<Moisture resistance>
The evaluation sheet was held for 100 hours under the conditions of 85 ° C. and 85% RH, and visually evaluated according to the following criteria.
○: Transparent △: Haze occurs

<Adhesion>
A sheet of 10 cm × 10 cm (thickness 1 mm) was affixed to a smooth PMMA plate, and the number of bubbles having a diameter of 2 mm or more was counted and evaluated according to the following criteria.
◎: Less than 5 ○: 5 or more and less than 10 Δ: 10 or more

<Surface smoothness>
The state of the surface of the cured film obtained by coating to 1 mm thickness and curing was visually evaluated.
○: Smooth with no unevenness Δ: Some unevenness occurs ×: All unevenness occurs

<Handability (brittleness)>
Using a tensile tester (manufactured by Instron), a test piece having a sheet width of 25 mm was pulled at a grip interval of 100 mm and a pulling speed of 300 mm / min, and the elongation rate until cutting was measured and evaluated according to the following criteria.
○: Elongation rate is 30% or more Δ: Elongation rate is 10% or more and less than 30% ×: Elongation rate is less than 10%

<Adhesive strength>
A 25 mm wide PET film (thickness: 25 μm) was attached to the evaluation sheet, and was subjected to one reciprocal pressure bonding with a 2 kg roller. The adhesive force when peeled in the 180 ° direction at a peeling speed of 300 mm / min within 1 minute after the pressure bonding was measured. These measurements were performed in an air atmosphere maintained at a constant temperature of 23 ° C.

From the results shown in Tables 3 to 5, when the component A (aliphatic (meth) acrylate oligomer) whose main chain is composed only of an aliphatic hydrocarbon skeleton is used (Comparative Examples 1 and 2), a molded body (sheet) It can be seen that the transparency is not sufficient, or the heat resistance and light resistance are not sufficiently high. Moreover, when an aromatic compound is used as A or B component (Comparative Examples 3-5), it turns out that the light resistance of a molded object does not become high enough. Further, when a component having a small weight average molecular weight (less than 1000) is used as the component A (Comparative Example 6), it is found that the molded body is brittle and inferior in handleability, and the adhesion and surface smoothness are not sufficiently increased. . Moreover, it turns out that sufficient handleability, surface smoothness, and adhesiveness are not acquired as a molded object does not contain A component (comparative example 7).

Example 31 (a form in which a protective film is provided and cut)
The resin composition (28) prepared in Preparation Example 28 was applied to a PET film (Lumirror T60, thickness 100 μm, manufactured by Toray Industries, Inc.) as a first protective film, and UV irradiation (high pressure mercury lamp, manufactured by USHIO INC.) And a dose (500 mJ / cm ² ) to obtain a layer (a) comprising the molded article of the present invention having a thickness of 400 μm. Furthermore, a molded body layer having a two-layer structure in which the resin composition (29) obtained in Preparation Example 29 was applied and cured under the same conditions to form a layer (b) having a thickness of 400 μm on the surface of the layer (a). Obtained. Next, laminating is performed in a state where the acrylic adhesive layer side of the acrylic adhesive-treated PET film (removable film GN75, thickness 75 μm, manufactured by Panac) as the second protective film is laminated on the surface of the layer (b). Thus, a sheet (31) obtained by laminating the second protective film / layer (b) / layer (a) / first protective film in this order was obtained. The adhesive strength of the layer (a) was 40 g / 25 mm, and the adhesive strength of the layer (b) was less than 5 g / 25 mm.
Subsequently, the sheet (31) was cut as follows.
That is, the second sheet is formed in a tape shape having a width of 5.0 mm by a Thomson punching method (a punching method using a punching blade in which 10 straight blades are arranged in parallel at intervals of 5.0 mm) with respect to the sheet (31). Cutting was performed from the protective film side.
As a result of confirming a cross section perpendicular to the longitudinal direction of the obtained cut sheet with a micrometer, the second protective film and the molded body layer (layer (b) / layer (a)) were all 4.95 to It was cut to a width of 5.05 mm, and the first protective film was cut to a thickness of 20 μm on the soft layer contact side. That is, the cut sheet is supported on a half-cut protective film (support) in a state where a large number of molded body layers (with a protective film) cut into a tape shape having a width of 5.00 mm are arranged in the longitudinal direction. , Confirmed to be fixed.

<Tape adhesion test>
Five tapes were prepared by cutting the sheets obtained in Examples 17 and 28 to 30 into a tape having a width of 5.0 mm and a length of 100 mm, respectively. In addition, the cut sheet obtained in Example 31 was cut so that the length of the formed body layer was 100 mm in a tape shape with the protective film disposed.
The tape of each example prepared as described above was placed on a 100 mm square glass plate every 10 mm (so that the width of the non-adhesive portion between the tapes was 5 mm), and each tape was straight. The tape was sequentially adhered so that a glass plate with 5 tapes arranged was obtained. The tapes of Examples 28 to 30 were adhered to the glass plate with the layer (a) side as the adhesive surface. The tapes of Examples 29 and 30 were adhered after the PET film was peeled off. Further, the tape of Example 31 is made of a glass sheet having a laminated molded body (layer (a)) side as an adhesive surface by peeling a laminated molded body provided with a second protective film from the first protective film in the cut sheet. Adhered to the plate.
When the arrangement state of the tape on the obtained glass plate was visually observed, the following results were obtained.
(Tape arrangement in Example 17)
Of the five, there are portions where all five are slightly bent in the length direction, and the width between any two tapes is not uniform.
(Tape arrangement in Examples 28-30)
Of the five, three are adhered in a state of excellent linearity without bending the tape. Some of the other two were non-linear.
(Tape arrangement in Example 31)
All five are adhered in a state where the tape is not bent and has excellent linearity.

Claims (3)

A molded body formed the aliphatic (meth) acrylate oligomer and fats Zokua acrylate monomer as an essential component,
The composition ratio (aliphatic (meth) acrylate oligomer / aliphatic acrylate monomer) of the aliphatic (meth) acrylate oligomer and the aliphatic acrylate monomer for forming the molded body is 30/70 by mass ratio. ~ 99/1,
The aliphatic (meth) acrylate oligomer is at least one selected from the group consisting of a urethane skeleton, an ester skeleton, an ether skeleton, a carbonate skeleton, and a (meth) acrylate (co) polymer skeleton in the main chain. Having a skeleton and a non-hydrocarbon group in the main chain and / or side chain,
When the aliphatic (meth) acrylate oligomer is a urethane (meth) acrylate oligomer having a urethane skeleton in the main chain, the urethane (meth) acrylate oligomer has a urethane skeleton and a (poly) ester skeleton in the main chain , ( A poly) carbonate skeleton and a (meth) acrylate-based (co) polymer skeleton selected from other organic skeletons having non-hydrocarbon groups,
The fatty Zokua acrylate-based monomer, and acryloyl groups in one molecule, a hydroxyl group, a urethane group (bond), ester group (bond), ether group (bond), carbonate or polar groups in group (bond) A monomer having
The molded product, wherein the aliphatic (meth) acrylate oligomer has a weight average molecular weight of 1,000 or more and 500,000 or less. The molded body according to claim 1, wherein the molded body is a molded body for an optical transmission body. A molded body resin composition containing an aliphatic (meth) acrylate oligomer and fats Zokua acrylate monomer as an essential component,
The composition ratio (aliphatic (meth) acrylate oligomer / aliphatic acrylate monomer) between the aliphatic (meth) acrylate oligomer and the aliphatic acrylate monomer in the composition is 30/70 to 99 / by mass ratio. 1 and
The aliphatic (meth) acrylate oligomer is at least one selected from the group consisting of a urethane skeleton, an ester skeleton, an ether skeleton, a carbonate skeleton, and a (meth) acrylate (co) polymer skeleton in the main chain. Having a skeleton and a non-hydrocarbon group in the main chain and / or side chain,
When the aliphatic (meth) acrylate oligomer is a urethane (meth) acrylate oligomer having a urethane skeleton in the main chain, the urethane (meth) acrylate oligomer has a urethane skeleton and a (poly) ester skeleton in the main chain , ( A poly) carbonate skeleton and a (meth) acrylate-based (co) polymer skeleton selected from other organic skeletons having non-hydrocarbon groups,
The fatty Zokua acrylate-based monomer, and acryloyl groups in one molecule, a hydroxyl group, a urethane group (bond), ester group (bond), ether group (bond), carbonate or polar groups in group (bond) A monomer having
The resin composition for molded bodies, wherein the aliphatic (meth) acrylate oligomer has a weight average molecular weight of 1,000 or more and 500,000 or less.