JPWO2010073649A1 - Adhesive adhesive composition, laminate and image display device - Google Patents

Abstract

In the present invention, (a) (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer (component a), (b) photopolymerizable compound (component b) and (c) photopolymerization initiator (c) Component) and an alkoxysilane having a photopolymerizable group as a photopolymerizable compound, and an adhesive composition comprising the photocured product of the adhesive composition The present invention relates to a laminate bonded by an adhesive layer, a method for producing the same, and an image display device using the laminate. The adhesive composition is a substrate and a film, particularly a light-transmitting inorganic substrate and a polarized light When the element or polarizing plate is bonded, the initial adhesion to the bonding material is good, and when the adhesive layer is cured by photocuring after bonding, the adhesion and durability are excellent, and the polarizing element Functionality layers such as In addition, the adhesive composition can be processed into a sheet-like adhesive because it is easy to handle and cut. It is easy to process and is suitable for adhesion of various laminated films or laminated plates used in electronic devices, etc., and an image display device using the laminated body has a very high display quality projection image with little display unevenness. can get.

Description

The present invention relates to an adhesive composition suitable for bonding when producing an optical member used in an image display device such as a liquid crystal display device, and a laminate and a display device using the same.

  In recent years, display performance such as definition and contrast of liquid crystal display devices has been remarkably improved, and great progress has been made in so-called durability such as resistance to severe environments and extension of usable drive time. Projection-type liquid crystal display devices have improved performance as well, but at the same time, new problems have occurred.

As a result of achieving a high-contrast projection image, unevenness derived from optical members, which could not be distinguished from conventional low-contrast images, has been observed. In particular, the effect of unevenness generated in the polarizing plate on the high-contrast projected image is remarkable, and the heat generated when light passes through the polarizing plate induces the thermal birefringence of the triacetyl cellulose film used as a protective plate. In combination with the physical thermal strain of the film, the triacetyl cellulose film, which is originally arranged so as not to affect the linearly polarized light, causes a phase difference and an optical axis that affect the linearly polarized light, causing unevenness in the projected image. turn into. A polarizing plate has a structure in which protective plates are bonded to both surfaces or one surface of a polarizing element.
In the present invention, the terms “substrate” and “film” are not strictly distinguished. The term “film” is usually used for flexible thin membranes. However, as in the above case, in the term “protection plate”, “plate” is used, but “triacetyl cellulose” used as a protection plate is generally called “film”, so The term “film” is used as follows. Accordingly, the film is used not only for a soft thin film but also for a thin film even if it is not so flexible. In addition, “substrate” or “plate” means a rigid plate-like molded body having relatively little flexibility, or little or no flexibility.

  In addition, the demand for miniaturization, high definition, and high brightness in the projection-type liquid crystal display devices has increased, and a high-power lamp has come to be selected. As a result, the film itself deteriorates. In order to solve these problems caused by the protective plate, there is a method of using a protective plate that is essentially resistant to thermal birefringence and has high heat resistance in place of the triacetyl cellulose film. Examples of the protective plate satisfying such properties include light transmissive inorganic substrates such as an inorganic glass plate, a crystal plate, and a sapphire plate.

  As a method of laminating a polarizing element and an inorganic substrate such as an inorganic glass plate, a crystal plate, or a sapphire plate, there is a method using a photo-curing adhesive having an advantage of minimizing the influence on an optical member that is vulnerable to high heat. preferable. Moreover, the method of using the adhesive suitable for the process of an optical member is mentioned. When the present inventors diligently studied to improve the problem of unevenness in the projected image, when the inorganic substrate is directly bonded to the polarizing element with a conventional photocurable adhesive or pressure-sensitive adhesive, a triacetylcellulose film is used. It was found that problems caused by the bonding layer, which cannot be seen in the polarizing plate used for the protective plate, occurred. That was a change in appearance and a deterioration in the performance of the polarizing element.

  A structure in which a polarizing plate or a polarizing element is bonded to an inorganic substrate such as inorganic glass, sapphire, or quartz is known as shown in Patent Documents 1-5. Patent Documents 1 and 2 disclose a configuration in which a sapphire plate is used as a polarizing plate holding plate. In order to prevent deterioration of the polarizing plate used in the projection type liquid crystal display due to light and heat, a sapphire substrate with high thermal conductivity is bonded to the polarizing plate with the intention of increasing the cooling efficiency of the air cooling fan, thereby improving the display quality. is there. However, there is no detailed description of the bonding layer, and the appearance change and long-term durability of the polarizing plate, which are regarded as problems by the present inventors, are not mentioned and are overlooked.

  Patent Document 3 discloses a configuration in which a substrate having high thermal conductivity is attached to one surface of the polarizing plate used in the projection type liquid crystal display device (the surface opposite to the liquid crystal light valve). Patent Document 4 discloses a configuration in which a glass plate is bonded to at least one surface of a polarizing element and combined with an ultraviolet cut filter. These techniques aim to increase the air cooling efficiency and prevent deterioration of the liquid crystal light valve and the polarizing plate, as in Patent Documents 1 and 2. However, there is no detailed description of the material regarding the bonding layer, and any problems caused by the bonding layer are overlooked.

  Patent Document 5 discloses a configuration in which an inorganic material is bonded to both surfaces of a polarizing plate. In the projection type liquid crystal display device, the polarization characteristics of the polarizing plate can be prevented from deteriorating, and by combining the sapphire plate or quartz substrate at an appropriate angle, the projection display quality is higher than when triacetyl cellulose is used as a protective plate. Is obtained. However, the use of a photo-curing adhesive or pressure-sensitive adhesive is only roughly described for bonding, and the problems caused by the bonding layer found by the present inventors are also overlooked.

  Conventional technology improves heat quality by attaching an inorganic substrate as a heat sink to a polarizing plate or polarizing element, improves the display quality of the projection-type liquid crystal display device, and suppresses thermal deterioration of the polarizing plate over time. In any case, problems caused by the bonding layer are overlooked.

Japanese Patent No. 3091183 (page 2-4) JP 2006-276617 A (page 2-4) Patent 3049752 (page 2-3) JP 10-39138 (page 2-4) JP2008-51995 (pages 3-6)

  In order to improve the problem of unevenness of the projected image, the present inventors have intensively studied the bonding of a light-transmitting inorganic substrate and a polarizing element. Since the compound of the adhesive layer affects the polarizing element and accelerates the deterioration, the durability as a polarizing plate tends to be remarkably lowered, and the adhesive layer is liable to be peeled off by curing shrinkage, while the conventional When a known pressure-sensitive adhesive is used, there is a problem that the pressure-sensitive adhesive layer is easily peeled off by heat, although the durability does not extremely decrease.

  Furthermore, in a polarizing plate using an inorganic substrate bonded with a conventionally known photocurable adhesive as a protective plate, the polarizing element heat shrinks, whereas the inorganic substrate hardly heat shrinks. Therefore, in the worst case, due to the temperature rise of the polarizing plate when the liquid crystal display device is used, there is a problem that the polarizing element is broken, the appearance of the bonding layer is deteriorated, and the performance of the polarizing plate is deteriorated. The deterioration of the appearance of the bonding layer and the deterioration of the performance due to the breaking of the polarizing element are problems that are strongly desired to be improved because the display performance of the projection type liquid crystal display device is obviously deteriorated.

  As a result of diligent research to solve the above problems, the present inventors have solved the above problem by adhering the inorganic plate to a polarizing element using an adhesive composition containing a specific component. The present invention has been completed. That is, the present inventors include (a) an acrylic adhesive component, (b) a photopolymerizable compound, and (c) a photopolymerization initiator, and the acrylic adhesive component is a C1-C12 alkyl (meth) acrylate. It has been found that an adhesive-adhesive composition comprising an ester-acrylamide copolymer and containing an alkoxysilane having a photopolymerizable group as a photopolymerizable compound is suitable for the above-mentioned adhesion. In addition, the (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer, which is the above-mentioned acrylic pressure-sensitive adhesive component, is a main component of (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms as the main component. 1 to 49% by weight of a polymerizable monomer having an amide group in the molecule, preferably an acrylamide monomer-derived component, as the other copolymer component. It was found that a (meth) acrylic acid ester-acrylamide copolymer contained in a proportion of% was preferable. Using the above-mentioned adhesive composition as an adhesive, a film (for example, a polarizing element) and an inorganic substrate (for example, a sapphire plate, a crystal plate, or a glass plate) are bonded together, and the inorganic substrate is used as a protective plate. In the case of producing a laminate, an adhesive layer of the adhesive composition is formed between the two, and after the two are adhered, the adhesive layer is irradiated with ultraviolet rays. The product laminate can be obtained by curing. By arranging the obtained laminate on the incident side, the emission side, or both sides of the liquid crystal light valve of the projection type liquid crystal display, a projection image with high display quality can be obtained and at the same time, it was seen with conventional adhesives The inventors have found that the deterioration of the durability of the polarizing plate, the peeling of the bonding layer, and the breakage of the polarizing element can be suppressed, and the present invention has been completed.

That is, the present invention relates to the following inventions.
(1) (a) (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer (component a), (b) photopolymerizable compound (component b) and (c) photopolymerization initiator (c) Component) and an alkoxysilane having a photopolymerizable group as a photopolymerizable compound.
(2) The adhesive composition according to (1), wherein the photopolymerizable group is at least one group selected from the group consisting of a (meth) acryl group, a vinyl group, and an epoxy group.
(3) The adhesive according to (1) or (2) above, wherein the alkoxysilane having a photopolymerizable group is a monomer or an oligomer obtained by condensation polymerization of 2 to 70 monomers. Sex composition.
(4) The content of the acrylamide monomer-derived component in the (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer is from 1 to 49% by weight based on the whole copolymer (1) to ( The adhesive composition according to any one of 3).
(5) Any of the above (1) to (4), which includes both an alkoxysilane having a photopolymerizable group and a photopolymerizable compound having two or more photopolymerizable groups in one molecule as the photopolymerizable compound. The adhesive composition according to claim 1.
(6) The adhesive composition according to (5), wherein the photopolymerizable compound having two or more photopolymerizable groups in one molecule is a di- or triacrylate compound.
(7) The content of the alkoxysilane having a photopolymerizable group is 0.5% by weight to 60% by weight with respect to the total amount of component a, component b and component c of the adhesive composition ( The adhesive composition according to any one of 1) to (6).
(8) The content of the photopolymerizable compound having two or more photopolymerizable groups in one molecule is 1% by weight with respect to the total amount of component a, component b and component c of the adhesive composition. The adhesive composition according to any one of (5) to (7), wherein the composition is 30% by weight.
(9) A laminate in which at least two substrates or two films, or a film and a substrate are bonded together by the photocured material layer of the blend composition according to any one of (1) to (8) above. body.

(10) Two substrates or two films, or one of the film and the substrate is a polarizing element or a polarizing plate, and the other is one selected from the group consisting of an inorganic glass plate, a quartz substrate and a sapphire substrate. The laminate according to (9) above.
(11) The laminate according to (10), wherein the polarizing element or polarizing plate is a dye-based polarizing element or a dye-based polarizing plate.
(12) Any of the above (9) to (11), wherein the film is an organic film selected from a cellulose film, a polyvinyl alcohol film, a polyester film, a cycloolefin film, a polyethylene terephthalate film, and an acrylic film. The laminate according to claim 1.
(13) An image display device using the laminate according to any one of (9) to (12) in an optical system.
(14) A projection-type liquid crystal display device in which the laminate according to any one of (9) to (13) is disposed on one or both of a light incident side and a light emitting side of a liquid crystal light valve.
(15) After bonding at least two substrates or two films, or a film and a substrate with the adhesive composition according to any one of (1) to (8) above, ultraviolet rays The method for producing a laminate according to any one of (9) to (14) above, wherein the layer of the adhesive composition is cured by irradiation.
(16) The adhesive composition according to 1 to 8, wherein the adhesive composition contains an organic solvent, and the amount of the organic solvent is 1 to 10 times the total amount of the component a, component b and component c. Wearing composition.

Since the adhesive composition of the present invention can be processed into a sheet-like adhesive, it is easy to handle and cut, easy to paste, and used in various electronic devices. It is suitable for adhesion of laminated films or laminated plates, and can contribute to improving the production efficiency of laminated bodies and reducing processing costs.
In addition, the adhesive compounding composition has good initial adhesion to the bonding material, excellent adhesion and durability after bonding, and may deteriorate a functional film to be laminated such as a polarizing element. It has excellent performance.
Moreover, the laminated body bonded together by the photocuring layer of the adhesive compounding composition of this invention, especially the laminated body in which the translucent inorganic board | substrate and the polarizing element or the polarizing plate were bonded together are used for a projection-type liquid crystal display device. Even when it is used, the laminate does not peel off due to the temperature rise of the laminate (for example, polarizing plate), and the laminated film (for example, polarizing element) does not break. In a projection-type liquid crystal display device using the above, a projected image with very high display quality with little display unevenness can be obtained. Furthermore, the adhesive layer composed of the photocured layer of the adhesive composition of the present invention does not deteriorate the performance of the attached functional film (for example, polarizing element), and the Since the adhesive layer has good durability against light and heat, the durability of a laminate such as a polarizing plate is also good.

It is a figure which shows an example of the laminated body of this invention. It is a figure which shows another example of the laminated body of this invention. It is a schematic diagram which shows an example which arrange | positions the laminated body (for example, polarizing plate) of this invention to the light valve vicinity (one side of a light valve) of a projection type liquid crystal display device, and arrange | positions the conventional polarizing plate to the other. It is a schematic diagram which shows another example which arrange | positions the laminated body (for example, polarizing plate) of this invention to the light valve vicinity (one side of a light valve) of a projection type liquid crystal display device, and arrange | positions the conventional polarizing plate to the other. . It is a schematic diagram which shows an example which arrange | positions the laminated body (for example, polarizing plate) of this invention one sheet each in the vicinity of the light valve of a projection type liquid crystal display device (both sides of a light valve). It is a schematic diagram which shows an example which arrange | positions the laminated body (for example, polarizing plate) of this invention continuously with the conventional polarizing plate in the light valve vicinity (incident side with respect to light) of a projection type liquid crystal display device. It is a schematic diagram which shows another example which arrange | positions the laminated body (for example, polarizing plate) of this invention continuously with the conventional polarizing plate in the light valve vicinity (incident side with respect to light) of a projection type liquid crystal display device. It is a schematic diagram which shows an example which arrange | positions the laminated body (for example, polarizing plate) of this invention continuously in the light valve vicinity (incident side with respect to light) of a projection type liquid crystal display device. It is a schematic diagram which shows the light resistance tester of the laminated body of this invention in connection with the Example of this invention. It is a schematic diagram which shows one example of the image display apparatus using the laminated body of this invention in connection with the Example of this invention, and the unevenness test machine of a projection image | video simultaneously.

The present invention will be described in detail.
In general, an adhesive is a bonding material that does not require the action of water, solvent, heat, etc., and can adhere materials together with a weak pressure like pressing with a finger, and can be peeled off again. Acrylic and urethane adhesives, rubber adhesives, silicon adhesives, and the like.

An acrylic pressure-sensitive adhesive is usually a copolymer of one or more types of (meth) acrylic acid or / and (meth) acrylic acid ester (hereinafter also referred to as an acrylic monomer), and the acrylic monomer as a main component. Accordingly, it is a general name for an adhesive mainly comprising a copolymer obtained by polymerizing with another copolymerizable vinyl monomer as a main component of the adhesive component, and is a combination of monomers used for copolymerization. Adhesives containing an adhesive component suitable for various purposes are known. These pressure-sensitive adhesives are usually used as pressure-sensitive adhesives in the form of a mixture with a solvent having a solid content of about 10 to 50% by weight.
The urethane-based pressure-sensitive adhesive is a pressure-sensitive adhesive included in the category of a so-called urethane-based pressure-sensitive adhesive whose main component is a polymer, elastomer, or oligomer containing one or more urethane bonds in the molecule.
The rubber-based pressure-sensitive adhesive is natural rubber mainly composed of cis-1,4-polyisoprene, styrene / butadiene rubber (SBR), synthetic rubber mainly composed of polyisobutylene, butyl rubber, or the like, or styrene / butadiene / A pressure-sensitive adhesive containing, as a main component of a pressure-sensitive adhesive component, an adhesive elastomer selected from at least one of block rubbers made of styrene copolymer rubber (SBS), styrene / isoprene / styrene copolymer rubber (SIS), etc. It is water or an organic solvent solution having a solid content, or water or an organic solvent dispersion.
The silicone-based pressure-sensitive adhesive includes a polysiloxane derivative as a main component, and examples thereof include a pressure-sensitive adhesive obtained by condensing a copolymer composed of SiO2 units and (CH2) 3SiO units and diorganopolysiloxane raw rubber.

As the pressure-sensitive adhesive in the adhesive composition containing an alkoxysilane having a photopolymerizable group, any of the above-mentioned pressure-sensitive adhesives may be used, or they may be used alone or in combination. .
In the present invention, an acrylic pressure-sensitive adhesive, in particular, a (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer is used as a pressure-sensitive adhesive component in view of wettability to the surface of the material to be bonded (adhered material) and initial adhesion. The pressure sensitive adhesive is preferred.
The (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer (component a) used as the adhesive component (a) in the adhesive composition of the present invention is a (meth) acrylic acid C1-C12 alkyl. A copolymer obtained by copolymerizing a monomer mixture mainly composed of an ester monomer and an acrylamide monomer may be used, but usually a component derived from a (meth) acrylic acid C1-C12 alkyl ester monomer A (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer is preferred. As the preferable copolymer, a component derived from a (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 12 carbon atoms ((meth) acrylic acid C1-C12 alkyl ester monomer) is used. A copolymer containing as a main component a component derived from a polymerizable monomer having an amide group in the copolymer molecule, preferably 1 to 49% by weight based on the total amount of the copolymer. Is preferred.
In addition, in the above, the meaning of containing as a main component means the most abundant component in a monomer component, and when the content of the acrylamide monomer-derived component is 1 to 49% by weight, (meth) The content of the acrylic acid C1-C12 alkyl ester monomer-derived component is 51 to 99% by weight based on the total amount of the copolymer.

Examples of the (meth) acrylic acid C1-C12 alkyl ester monomer used in the copolymer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth) N-propyl acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, dodecyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl, or isononyl (meth) acrylate, and (meth) acrylic acid hydroxy C1-C12 alkyl esters having hydroxy substitution on the alkyl groups of these compounds, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate or 4-hydroxybutyl ( Data) hydroxy-substituted a can be mentioned may also be C1-C12 alkyl (meth) acrylates having such acrylates.
Among them, preferable examples include (meth) acrylic acid C1-C4 alkyl ester monomers. Specifically, the (meth) acrylic acid C1-C4 alkyl esters exemplified above and (meth) ) Acrylic acid hydroxy C1-C4 alkyl ester and the like.
In addition, the (meth) acrylic acid C1-C12 alkyl ester monomer used in the copolymer may be one type, but is usually a (meth) acrylic acid C1-C12 alkyl ester monomer, preferably It is preferable to use 1 to 4 types, preferably 2 to 4 types, of (meth) acrylic acid C1-C4 alkyl ester monomers. As a combination of the (meth) acrylic acid C1-C12 alkyl ester monomer, 1 to 3 kinds of (meth) acrylic acid C1-C12 alkyl ester (preferably (meth) acrylic acid C1-C4 alkyl ester), and , (Meth) acrylic acid hydroxy C1-C12 alkyl ester 1-2 types, preferably 1 type is preferably used in combination. In this case, the (meth) acrylic acid hydroxy C1-C12 alkyl ester is preferably a (meth) acrylic acid hydroxy C1-C4 alkyl ester. More preferably, 1 to 3 kinds of acrylic acid C1-C4 alkyl esters and 1 kind of acrylic acid hydroxy C1-C4 alkyl ester are used in combination. In the case of using these hydroxyalkyl esters in combination, when the amount of (meth) acrylic acid C1-C12 alkyl ester (preferably acrylic acid C1-C4 alkyl ester) is 100 parts by weight, (meth) acrylic acid hydroxy C1-C12 alkyl ester (Preferably, hydroxy C1-C4 alkyl ester of acrylic acid) It is preferably used in a proportion of 0.5-5 parts by weight.
In the present specification, the term “(meth) acryl” is used in the meaning of “acryl or / and methacryl”, which means that either acryl or methacryl may be used. For example, “methyl (meth) acrylate” is used in the meaning that either methyl acrylate or methyl methacrylate may be used.

Polymerizable monomers having an amide group in the molecule, preferably acrylamide monomers include acrylamide, N-mono or N, N-di (C1-C6 alkyl) acrylamide, acrylic C5-C6 cyclic amide, or N -Mono or N, N-di (hydroxy C1-C6 alkyl) acrylamide etc. can be mentioned. Specifically, for example, N- (N ′, N′-dimethylamino) propylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, acryloylmorpholine, N-isopropylacrylamide, N-methylolacrylamide, acrylamide, etc. Acrylamide monomer. Preferred acrylamide monomers include acrylamide, or N mono or N, N-di (C1-C4 alkyl) acrylamide, and more preferably N, N-di (C1-C4 alkyl) acrylamide. These may be used in combination of 2-3 types, but usually one type.
The (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer (component a) is obtained by subjecting a single amount of (meth) acrylic acid C1-C12 alkyl ester and an acrylamide monomer to conventional methods such as solution polymerization or suspension polymerization. It can be obtained by copolymerization.

The polymerization degree of the (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer of the above-mentioned acrylic adhesive component is not particularly limited as long as it has a degree of polymerization having a function as an adhesive component, but usually gel permeation chromatography ( GPC) has a weight average molecular weight of about 500,000 to 2,500,000, preferably about 700,000 to 2,000,000, more preferably about 700,000 to 1,800,000, still more preferably. 700,000 to 1,500,000.
Moreover, as a preferable composition of the (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer, the component derived from the (meth) acrylic acid C1-C12 alkyl ester monomer is 70- to the total amount of the copolymer. 98% by weight, the acrylamide monomer-derived component is 2-30% by weight, and more preferably, the (meth) acrylic acid C1-C12 alkyl ester monomer-derived component is 80-98% by weight. The monomer-derived component is 2-20% by weight, more preferably, the (meth) acrylic acid C1-C12 alkyl ester monomer-derived component is 90-98% by weight, and the acrylamide monomer-derived component is 2%. -10% by weight.
The content of the (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer as the adhesive component in the adhesive compounding agent of the present invention is the total amount of the components a, b and c of the adhesive compounding agent. In contrast, it is the remainder of the contents of component b and component c described later, preferably about 50 to 90% by weight, more preferably 60 to 90%, based on the total amount of component a, component b and component c. It is about wt%, more preferably about 60 to 85 wt%.

As described above, the adhesive composition of the present invention comprises (a) a (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer (component a), (b) a photopolymerizable compound ( b component) and (c) a photopolymerization initiator (c component) and an alkoxysilane (b-1 component) having a photopolymerizable group as a photopolymerizable compound.
The adhesive composition is appropriately mixed with the above (a) (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer, (b) a photopolymerizable compound, and (c) a photopolymerization initiator. However, it can be usually obtained in the presence of a solvent by mixing to obtain the adhesive composition containing the solvent.
The (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer as the above-mentioned (a) adhesive component may be used directly in the production of the adhesive composition of the present invention. However, the reaction solution containing the (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer used in the present invention obtained by copolymerization of the corresponding monomer is adjusted to an appropriate concentration by a conventional method. You may use it for the adhesive compounding composition of this invention as an adhesive.

The acrylic pressure-sensitive adhesive used in the present invention may be a pressure-sensitive adhesive containing only the (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer alone, but if necessary, a crosslinking agent is added. Then, it may be used as a crosslinkable pressure-sensitive adhesive.
The crosslinking agent used in the above-mentioned pressure-sensitive adhesive is not particularly limited as long as it is a conventional one for acrylic pressure-sensitive adhesives. For example, polyisocyanate compounds such as aliphatic diisocyanate and aromatic diisocyanate, butyl etherified styrol melamine, trimethylol melamine Melamine compounds such as epoxy resins, silane coupling agents, coupling agents with metal complexes, metal salts, and the like are used.
Among these, preferable examples include a silane coupling agent, and specifically, mention may be made of the alkoxysilane compounds mentioned as the alkoxysilane compounds having a photopolymerizable group described later used in the present invention. I can do it. More preferably, it is an alkoxysilane compound having an epoxy group. For example, as a preferable alkoxysilane compound compound, glycidoxy C1-C5 alkyl (triC1-C4 alkoxy) silane such as γ-glycidoxypropyltrimethoxysilane is preferable.
The amount of the crosslinking agent used in the pressure-sensitive adhesive is 0.001 to 10 parts by weight, preferably 100 parts by weight of the above-mentioned pressure-sensitive adhesive component, specifically (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer, The ratio is about 0.005 to 5 parts by weight, more preferably about 0.01 to 5 parts by weight.

Examples of the isocyanate compound used as a crosslinking agent in the above include tolylene diisocyanate, hydrogenated tolylene diisocyanate, tolylene diisocyanate adduct of trimethylol propane, xylylene diisocyanate adduct of trimethylol propane, trimethylol propane adduct hexamethylene diene. Examples thereof include isocyanate (Coronate ^RTM HL: manufactured by Nippon Polyurethane Industry Co., Ltd.), triphenylmethane triisocyanate, methylenebis (4-phenylmethane) triisocyanate, isophorone diisocyanate, and the like, and ketoxime block products or phenol block products thereof. .
Examples of epoxy resin compounds include bisphenol A / epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, Examples thereof include diglycidylamine, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N′-diglycidylaminoethyl) cyclohexane and the like. Examples of metal salts include aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and other polyvalent metal chlorides, bromides, nitrates, sulfates, acetates, and the like. Specific examples include cupric chloride, aluminum chloride, ferric chloride, stannic chloride, zinc chloride, nickel chloride, magnesium chloride, aluminum sulfate, copper acetate, and chromium acetate.

As a photopolymerizable compound used in the present invention, one molecule of an alkoxysilane compound (component b-1) having a photopolymerizable group and a photopolymerizable group (specifically, an ethylenically unsaturated double bond) is used. The compound (b-2 component) which has at least 1 or more in it can be mentioned. The adhesive composition according to the present invention includes at least an alkoxysilane (b-1 component) having a photopolymerizable group.
The alkoxysilane having a photopolymerizable group acts as an adhesion component to the films to be bonded to each other, to the substrates, or to both the film and the substrate, and improves the initial adhesion after the bonding operation. Further, the alkoxysilane is polymerized together with a photopolymerizable compound having another photopolymerizable group, which will be described later, which is used in combination as necessary by photopolymerization, and the adhesive component of the adhesive used in the present invention is strong. It is physically or / and chemically bonded to the material, and develops a function of increasing the physical strength of the blended composition itself. By these actions, the adhesive composition according to the present invention can achieve continuous adhesion that cannot be achieved with conventional adhesives and pressure-sensitive adhesives, and durability under severe conditions.

The photopolymerizable group in the alkoxysilane compound (b-1 component) having the photopolymerizable group has any one of (meth) acrylic group (acrylic group or methacrylic group), vinyl group, and epoxy group. Is preferred.
Examples of such a photopolymerizable compound include vinyl C1-C4 alkoxysilanes such as vinyltrimethoxysilane or vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacrylic silane. (Meth) acryloyloxy C1-C4 alkyltri-C1-C4 alkoxysilane, p-styryltrimethoxysilane, such as loxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, or 3-acryloxypropyltrimethoxysilane N- (vinylbenzyl) amino C1-C5 alkylamino C such as styryltri C1-C4 alkoxysilane, hydrochloride of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane -C5 alkyltri C1-C4 alkoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and other epoxycyclohexyl C1-C4 alkyltriC1-C4 alkoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxy C1-C4 alkyl tri-C1-C4 alkoxysilane such as glycidoxypropylmethyldiethoxysilane or 3-glycidoxypropyltriethoxysilane, alkoxysilane having a (meth) acryl group (for example, the (meth) acryloyloxy) C1-C4 alkyltri C1-C4 alkoxysilane) dimer, trimer or tetramer or higher alkoxysilane oligomer etc. (meth) acryloyloxy C1-C4 alkyltri C1-C4 alkoxysilane 2-70 amount Degree of oligomerization, oligomers of about 2-70 mers of alkoxysilane having an epoxy group (e.g., the glycidoxy C1-C4 alkyl tri C1-C4 alkoxy silane) and the like.
Among these, (meth) acryloyloxy C1-C4 alkyltri-C1-C4 alkoxysilane or an oligomer thereof (about 2-70 mer) is more preferable.
In addition, when the alkoxysilane compound which has a photopolymerizable group is used as said crosslinking agent in said adhesive, in the adhesive compounding composition of this invention, b-1 component alkoxy for convenience. Treat as silane and calculate content as b-1 component.

  Commercially available products are Shin-Etsu Chemical KBM-1003, KBE-1003, KBM1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-575, KBM-303, KBM-403, KBE-402, KBE-403, X-41-1053, X-41-1056, X-40-9271, X-40-2655A, Chisso Corporation Sila Ace S210, Sila Ace S220, Sila Ace S710, Sila Ace S350, Sila Ace S510, Sila Ace S530, Silaplane FM-4411, Silaplane FM-7711, Silaplane FM-0711, Silaplane TM-0701, etc. are on the market. Any of them can be used in the present invention, but (meth) acryloyloxy C1-C4 alkyltri-C1-C4 alkoxysilane is preferable.

Examples of a compound having at least one ethylenically unsaturated double bond in one molecule (hereinafter referred to as an ethylenically unsaturated double bond-containing compound) (component b-2) include (meth) acrylic acid, itacon Unsaturated carboxylic acids such as acids, crotonic acid, isocrotonic acid, maleic acid and their derivatives, vinyl ethers and derivatives thereof, and oligomers and polymer compounds such as unsaturated polyesters, unsaturated polyethers, unsaturated polyamides and unsaturated polyurethanes Is mentioned. One or more kinds of these general ethylenically unsaturated double bond-containing compounds may be added.
In the present invention, as the ethylenically unsaturated double bond-containing compound, any compound having one ethylenically unsaturated double bond and having two or more ethylenically unsaturated double bonds can be used. In the adhesive composition of the present invention, when an ethylenically unsaturated double bond-containing compound includes a compound having two or more ethylenically unsaturated double bonds, one ethylenically unsaturated double bond is included. It is more preferable than the case where the compound which has one is included, and the outstanding performance of the said this invention is exhibited more.
Specific examples of those having an ethylenically unsaturated double bond include the following compounds.

Compound having one ethylenically unsaturated double bond:
Tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, Phenoxyhydroxypropyl (meth) acrylate, acryloylmorpholine, methoxypolyethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxyethyl (meth) Acrylate, glycidyl (meth) acrylate, glycerol (meth) acrylate, Eth Carbitol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, reaction product of butyl glycidyl ether and (meth) acrylic acid , Butoxytriethylene glycol (meth) acrylate, butanediol mono (meth) acrylate, and the like.

Compounds having two ethylenically unsaturated double bonds:
Allylated cyclohexyl diacrylate, bis (acryloxyethyl) hydroxyethyl isocyanurate, bis (acryloxy neopentyl glycol) adipate, EO-modified bisphenol A di (meth) acrylate, EO-modified bisphenol S diacrylate, EO-modified bisphenol F diacrylate Bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, di Cyclopentanyl diacrylate, diethylene glycol di (meth) acrylate, ECH-modified diethylene glycol dimethacrylate, ECH-modified ethylene glycol di (meth) acrylate , Ethylene glycol dimethacrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 1,6-hexanediol di (meth) acrylate, ECH modified 1,6-hexanediol diacrylate, long chain aliphatic di (meth) acrylate, methoxy Cyclohexyl diacrylate, neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol diacrylate, caprolactone-modified hydroxypivalate neopentyl glycol diacrylate, stearic acid-modified pentaerythritol diacrylate, EO-modified phosphate di (meth) Acrylate, caprolactone, EO-modified phosphate dimethacrylate, ECH-modified phthalic acid diacrylate, polyethylene glycol di (me ) Acrylate, polypropylene glycol di (meth) acrylate, ECH modified propylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, tetrabromobisphenol A diacrylate, triethylene glycol di (meth) acrylate, triethylene glycol divinyl ether, tri Glycerol diacrylate, neopentyl glycol modified trimethylolpropane diacrylate, tripropylene glycol diacrylate, triglycerol di (meth) acrylate, reaction product of propylene glycol diglycidyl ether and (meth) acrylic acid, polypropylene glycol di (meth ) Acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) ) Acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, reaction product of 1,6-hexanediol diglycidyl ether and (meth) acrylic acid, 1,6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, reaction product of ethylene glycol diglycidyl ether and (meth) acrylic acid, reaction product of diethylene glycol diglycidyl ether and (meth) acrylic acid Products, bis (acryloxyethyl) hydroxyethyl isocyanurate, bis (methacryloxyethyl) hydroxyethyl isocyanurate, reaction products of bisphenol A diglycidyl ether and (meth) acrylic acid, and the like.

Compound having three ethylenically unsaturated double bonds:
Dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, alkyl modified dipentaerythritol pentaacrylate, alkyl modified dipentaerythritol tetraacrylate, alkyl modified dipentaerythritol triacrylate, caprolactone modified dipentaerythritol hexaacrylate, ECH modified glycerol tri Acrylate, pentaerythritol triacrylate, pentaerythritol tetra (meth) acrylate, EO modified phosphoric acid triacrylate, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane triacrylate, PO modified trimethylolpropane triacrylate, ECH modified tri Methylolpropane triacre relay , Tris ((meth) acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, zinc di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexa Acrylate, reaction product of pentaerythritol tri (meth) acrylate and 1,6-hexamethylene diisocyanate, reaction product of pentaerythritol tri (meth) acrylate and isophorone diisocyanate, tris (acryloxyethyl) isocyanurate, tris ( (Methacryloxyethyl) isocyanurate, reaction product of glycerol triglycidyl ether and (meth) acrylic acid, caprolactone modified tris (acrylic) Kishiechiru) isocyanurate, the reaction product of trimethylol propane triglycidyl ether (meth) acrylate.
Among the components (b-2) mentioned above, preferred compounds in the present invention are di- or triacrylate compounds having 2 or 3 (meth) acryl groups. In particular, bisphenol di (meth) acrylate is more preferable.

As content of the alkoxysilane (b-1 component) which has a photopolymerizable group, it is 0.5 weight normally with respect to the total amount of a component, b component, and c component of the adhesive compounding composition of this invention. % To 60% by weight, preferably 1% to 50% by weight, more preferably 2% to 40% by weight, and still more preferably 3% to 40% by weight. Most preferably, it is 3 to 25% by weight.
As the ethylenically unsaturated double bond-containing compound (component b-2), a polyfunctional compound having two or more (meth) acryl groups is preferable, and the content of the compound is the adhesive composition of the present invention. It is usually in the range of 0.5 to 30% by weight, preferably 1 to 30% by weight, more preferably 1 to 10% by weight based on the total amount of the a component, b component and c component of the product. %, More preferably 1 to 6% by weight.
As the component b (total amount of the alkoxysilane b-1 component and the ethylenically unsaturated double bond-containing compound b-2 component) in the adhesive composition of the present invention, the a component and the b component are used. And c is usually 2 to 80% by weight, preferably 2.5 to 60% by weight, more preferably 3 to 40% by weight, still more preferably 3% by weight based on the total amount of component c and c. % To 30% by weight. In some cases, 4 wt% to 30 wt% is most preferable.
The ratio of the b-1 component and the b-2 component is 1 to 20 parts by weight of the b-1 component (the above alkoxysilane) with respect to 1 part by weight of the b-2 component (ethylenically unsaturated double bond-containing compound). A ratio of 1 to 15 parts by weight is preferred.

  When the alkoxysilane is contained in the above-mentioned range in the adhesive composition of the present invention, not only the initial adhesion when the inorganic substrate and the film are bonded is particularly good. Even when high temperature conditions of 120 ° C, so-called accelerated tests and severe environmental tests are performed such as 60 ° C 90% RH, 65 ° C 95% RH, 80 ° C 90% RH, 85 ° C 85% RH, etc. High adhesion can be maintained over a long period of time.

As the photopolymerization initiator used in the present invention, a compound used for ordinary ultraviolet curable polymerization can be used. Specific examples of compounds that can be used include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.), 1-hydroxycyclohexyl phenyl ketone ( Irgacure 184), 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone (Irgacure 2959), 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane -1-one (Darocur 953 manufactured by Merck & Co., Inc.), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (same Darocur 1116), 2-hydroxy-2-methyl-1- Phenylpropan-1-one (Ciba Specialty Chemicals Co., Ltd.) Substituted C1-C12 alkyl phenyl ketone compounds (substituent hydroxy, C1-C4 alkylthio, hydroxy C1-C4 alkoxy, etc.); acetophenone compounds such as diethoxyacetophenone; benzoin, benzoin methyl ether, benzoin ethyl ether Benzoin compounds such as benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651); benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl 4'-methyl-diphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone (manufactured by Nippon Kayaku Co., Ltd. KAYACURE ^RTM MB ) Benzophenone compounds such as; thioxanthone, 2-black Lucio hexane Son (same Kayacure ^RTM CTX), 2-methyl thioxanthone, 2,4-dimethyl thioxanthone (Kayacure ^RTM RTX), isopropyl thioxanthone, 2,4 Thioxanthone compounds such as diclothiothioxanthone (same Kayacure ^RTM CTX), 2,4-diethylthioxanthone (same Kayacure ^RTM DETX), 2,4-diisopropylthioxanthone (same Kayacure ^RTM DITX); 2, 4, 6 -Phosphine oxide compounds such as trimethylbenzoyldiphenylphosphine oxide (trade name; Speed Cure TPO, manufactured by Ramson Fire Chemical Co., Ltd.) and the like. These photopolymerization initiators may be used alone or in combination at any ratio. A substituted C1-C12 alkyl phenyl ketone compound or a phosphine oxide compound is preferred.

When a benzophenone compound or a thioxanthone compound is used, an auxiliary agent can be used in combination in order to promote the photopolymerization reaction. Examples of such auxiliaries include triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, n-methyldiethanolamine, diethylaminoethyl methacrylate, Michler's ketone, 4,4′-diethylaminophenone, 4-dimethylaminobenzoic acid. Examples include amine compounds such as ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, and 4-dimethylaminobenzoic acid isoamyl.
The content of the photopolymerization initiator is preferably 0.01 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the total amount of component a, component b and component c of the adhesive composition of the present invention. More preferably, the ratio is 0.1 parts by weight or more and 5 parts by weight or less. Further, the auxiliary agent is preferably about 0.5 to 2 times the amount of the photopolymerization initiator.
In addition, the adhesive composition of the present invention preferably includes a curing catalyst such as dibutyltin dilaurate. The curing catalyst is preferably about 0.001 to 0.1% by weight with respect to the total amount of component a, component b and component c of the adhesive composition of the present invention, and is preferably 0.01 to 0.04. %.

The adhesive composition of the present invention usually contains an organic solvent for the convenience of handling. The organic solvent in the adhesive composition of the present invention may be any of hydrocarbon-based, alcohol-based, ketone-based, ester-based, ether-based, and nitrogen-containing organic solvents. Preferable examples include ester solvents such as ethyl acetate, and aliphatic ketones having 3 to 5 carbon atoms such as methyl ethyl ketone. The amount of the solvent is 0.5 to 10 times by weight relative to the total amount of the component a, the photopolymerizable compound b component and the photopolymerization initiator c component in the adhesive composition of the present invention, preferably 1 to 10 times by weight, more preferably about 1 to 8 times by weight. When the solvent is included, the total content of the component a, the component b, and the component c in the adhesive composition of the present invention is 5 to 50 weights with respect to the total amount of the adhesive composition containing the solvent. %, More preferably about 10 to 30% by weight.
Moreover, it is preferable that the adhesive composition of this invention contains a crosslinking agent further. As the crosslinking agent, any of the crosslinking agents mentioned in the section of the pressure-sensitive adhesive can be used. The cross-linking agent may be the same as or different from the cross-linking agent in the pressure-sensitive adhesive. As the crosslinking agent to be added in the adhesive composition of the present invention, the isocyanate compounds mentioned in the section of the crosslinking agent in the pressure-sensitive adhesive are preferable.
The content of the crosslinking agent is a ratio of about 0.01 to 0.1 parts by weight with respect to 100 parts by weight of the total amount of component a, component b and component c in the adhesive composition of the present invention.

Any additive can be added to the adhesive composition of the present invention depending on the purpose of use and the like. Additives include natural polymers such as casein and starch, synthetic polymers such as melamine resins, phenolic resins and vinyl acetate resins, tackifiers such as rosin and terpene resins, phthalates, adipates, and phosphates. And the like, plasticizers such as methyl cellulose, cellulose acetate, and sodium alginate, phenolic, amine-based, sulfur-based, phosphorus-based antioxidants, hindered amine-based antioxidants, and the like. One type may be selected and added from these, or two or more types may be used in combination. These are 0 to 20% by weight, preferably 0 to 10% by weight, based on the total amount of component a, component b and component c in the adhesive composition of the present invention.
In addition, when the adhesive composition of the present invention is used in an optical system, it is preferable that it does not include a filler that normally inhibits light transmission, such as a filler.

Preferable examples of the adhesive composition of the present invention described above include the following.
1. (A) (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer (component a), (b) photopolymerizable compound (component b) and (c) photopolymerization initiator (component c) as the adhesive component And an alkoxysilane having a photopolymerizable group (b-1 component) as a photopolymerizable compound, and the content ratio of the b component with respect to the total amount of the a component, the b component, and the c component is from 2% by weight to 80% An adhesive composition having a weight percent of c, a component c content of 0.01% by weight to 10% by weight, and the balance being a component.
2. 2. The adhesive according to 1 above, wherein the content of the alkoxysilane (b-1 component) having a photopolymerizable group is 2% by weight or more and 40% by weight or less with respect to the total amount of the component a, component b, and component c. Sex composition.
3. Any one of the above 1-2, wherein the alkoxysilane (b-1 component) having a photopolymerizable group is (meth) acryloyloxy or glycidoxy C1-C4 alkyltri-C1-C4 alkoxysilane or a 2-70-mer oligomer thereof. The adhesive composition according to item.
4). As a photopolymerizable compound (component b), an alkoxysilane having a photopolymerizable group (component b-1) and a photopolymerizable compound having two or more photopolymerizable groups in one molecule (component b-2) 4. The adhesive composition according to any one of 1 to 3 above, comprising both.
5. The content of the photopolymerizable compound (b-2 component) having two or more photopolymerizable groups in one molecule is 1% by weight or more and 30% by weight with respect to the total amount of the a component, b component and c component. 5. The adhesive composition according to the above item 4, which is the following.
6). The weight ratio of the alkoxysilane (b-1 component) having a photopolymerizable group and the photopolymerizable compound (b-2 component) having two or more photopolymerizable groups in one molecule is 1 wt. The adhesive composition according to 4 or 5 above, wherein the b-1 component is 1 to 20 parts by weight relative to parts.

7). The adhesive according to any one of 4 to 6, wherein the photopolymerizable compound (component b-2) having two or more photopolymerizable groups in one molecule is a di- or tri (meth) acrylate compound. Sex composition.
8). The (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer (component a) comprises (meth) acrylic acid C1-C12 alkyl ester monomer-derived component 70 to 98% by weight and acrylamide monomer-derived component 2 The adhesive composition according to any one of 1 to 7 above, which is a 30% copolymer.
9. The (meth) acrylic acid C1-C12 alkyl ester monomer comprises (meth) acrylic acid C1-C12 alkyl ester and (meth) acrylic acid (hydroxy C1-C12 alkyl) ester, and (meth) acrylic acid C1- 9. The adhesive composition according to 8 above, wherein the amount of (meth) acrylic acid (hydroxy C1-C12 alkyl) ester is 0.5-5 parts by weight relative to 100 parts by weight of the C12 alkyl ester.
10. As an alkoxysilane having a photopolymerizable group (b-1 component), both alkoxysilane having a (meth) acryl group and an alkoxysilane having an epoxy group, the content ratio of which is an alkoxysilane 100 having a (meth) acryl group 10. The adhesive composition according to any one of 1 to 9 above, wherein the alkoxysilane having an epoxy group is 0.01 to 1 part by weight relative to parts by weight.
11. The alkoxysilane having a (meth) acryl group is a (meth) acryloyloxytri C1-C4 alkoxysilane or a 2-70-mer oligomer thereof, and the alkoxysilane having an epoxy group is a glycidoxy C1-C4 alkyltri-C1-C4 alkoxysilane. 11. The adhesive composition according to the above item 10, wherein
12 The adhesive composition includes an organic solvent, and the amount of the organic solvent is 2 to 6 times the total amount of the component a, the component b, and the component c. An adhesive composition.

The manufacturing method of the laminated body of this invention is demonstrated.
The laminate of the present invention comprises two substrates or films, or both of a film and a substrate bonded together with the adhesive composition of the present invention, and then the adhesive composition sandwiched between the two. It can be obtained by curing the adhesive composition layer by irradiating the layer with ultraviolet rays. Further, if necessary, by repeating this operation, a laminate in which three or more substrates or / and films are laminated can be obtained.
More specific description will be given below.
Various conventionally known methods can be used to bond both of the above-mentioned films and substrates with the adhesive composition of the present invention. For example, the adhesive composition of the present invention is directly applied to the bonding surface of the film or substrate to be bonded, and the adhesive composition is bonded so that the adhesive composition is sandwiched. Examples thereof include a method in which the adhesive composition is sandwiched between two sheets of the film having the film, processed into a sheet shape, and affixed to the bonding surface while peeling the release film.
As described above, the obtained laminate having the adhesive compounding composition layer is pressurized from both sides as necessary to sufficiently adhere (pressure-sensitive treatment). You can push it manually, or you can use a laminator or a laminator that can evenly load the entire surface. This operation is repeated as necessary to produce a laminate having the uncured adhesive layer of the present invention.

When a phenomenon that impairs the appearance such as air mixed into the bonding layer is observed, it is preferable to further improve by adding a pressure-sensitive treatment, a pressure reduction treatment or a pressure treatment, a heating treatment, and the like. Thereafter, the uncured adhesive layer sandwiched between the layers is irradiated with ultraviolet rays to perform photopolymerization, thereby curing the adhesive layer. A preferable irradiation amount varies depending on the type of the composition, the type and addition amount of the photopolymerization initiator, the film thickness, and the like, but is preferably about 50 to 50000 mJ / cm ² . Moreover, the atmosphere at the time of ultraviolet irradiation may be air or an inert gas such as nitrogen. As the ultraviolet irradiator, either a method of setting the irradiation target under the lamp or a method of moving the irradiation target with a belt conveyor or the like to pass under the lamp may be used. Moreover, if it is in the range of preferable irradiation amount, it is possible to irradiate as many times as necessary at once or to irradiate several times. Moreover, when setting it as the laminated board on which many films or a board | substrate was laminated | stacked, it can obtain by performing said operation repeatedly.
By this operation, the laminate of the present invention in which at least two substrates or films, or the film and the substrate are bonded together by the photocured material layer of the adhesive composition of the present invention is completed.

The ultraviolet irradiation is preferably performed in an amount that sufficiently cures the uncured adhesive layer. Albeit slightly different by a substrate or a film to be bonded together, usually 1000mJ ^/ cm ² ~20000mJ ^/ cm 2, preferably about 1500mJ ^/ cm ² ~10000mJ ^/ cm 2, more preferably about 2000mJ ^/ cm 2 ~5000mJ ^/ cm about ^2, more preferably it is preferred to irradiate about ^{2000mJ / cm 2 ~4500mJ / cm 2} .
In this way, by curing the uncured adhesive layer, the cured adhesive layer and the laminate of the present invention have excellent physical durability and adhesion under severe conditions. Excellent durability can be obtained.

  Examples of the film constituting the laminate of the present invention include a cellulose film, a polyvinyl alcohol film, a polyester film, a cycloolefin film, a polyethylene terephthalate film, and an acrylic film. Examples of the cellulose film include cellulose acylate films such as diacetyl cellulose, triacetyl cellulose, and cellulose acetate propionate. A polyvinyl alcohol-type film is a film normally formed from a polyvinyl alcohol-type resin. Examples of the polyvinyl alcohol resin include a saponified product obtained by saponifying a polyvinyl acetate generally obtained by polymerization of vinyl acetate in a lower alcohol solvent with a saponification catalyst such as an alkali or an acid, or a derivative thereof. In addition, modified polyvinyl alcohol resins obtained by saponifying a copolymer obtained by copolymerizing vinyl acetate as a main component and other copolymerizable monomers are also included in the polyvinyl alcohol resin.

Examples of the cycloolefin film include a norbornene film. Examples of the film include a resin obtained by ring-opening polymerization or ring-opening copolymer of a norbornene monomer, a resin obtained by addition polymerization of a norbornene monomer, and a norbornene monomer and an olefin monomer such as ethylene or α-olefin. And a film made of a resin obtained by addition copolymerization. The polyethylene terephthalate film is a polymer film made of a PET (polyethylene terephthalate) resin which is a crystalline thermoplastic polyester obtained by subjecting ethylene glycol and terephthalic acid to a polycondensation reaction.
Usually, it is crystallized by biaxially stretching and orienting molecules after film formation.

  As an acrylic resin film, a homopolymer of (meth) acrylic monomer ((meth) acrylic acid or (meth) acrylic ester) or a copolymer of two or more (meth) acrylic monomers, or at least one kind The film etc. which consist of a copolymer of a (meth) acryl monomer and another polymerizable monomer are mentioned. In addition, a silicone resin mainly composed of a polyorganosyl seroxyoxane having a cage structure in a structural unit having a (meth) acryloyl group, and -R1-CR2 = CH2 or -CR2 = CH2 ( Provided that R1 represents an alkylene group, an alkylidene group, or an —OCO— group, and R2 represents hydrogen or an alkyl group), and is capable of radical copolymerization with the silicone resin. Examples thereof include a film obtained from a composition characterized by blending an unsaturated compound in a weight ratio of 1:99 to 99: 1.

  One preferable example of the laminate of the present invention is a polarizing plate. When the laminate of the present invention is a polarizing plate, the polarizing element (polarizer) used for the polarizing plate is not particularly limited as long as it is a device having a function of polarizing light from a light source, and emits light in a specific direction. Either an absorptive polarizing element that absorbs polarized light and a reflective polarizing element that reflects light in a specific direction to polarize can be used. As an absorptive polarizing element, for example, a polarizing element obtained by uniaxially stretching a hydrophilic polymer film such as a polyvinyl alcohol film containing a dichroic dye such as a dye or polyvalent iodine ion, a polyvinyl alcohol film A polarizing element obtained by dehydrating with an acid before and after uniaxial stretching to form a polyene structure, and a solution of a dichroic dye that develops a lyotropic liquid crystal state on an alignment film that has been processed to align in a certain direction Examples thereof include a polarizing element obtained by applying and then removing the solvent. On the other hand, as a reflective polarizing element, for example, a polarizing element composed of a large number of laminated bodies having different birefringence, a polarizing element formed by combining a cholesteric liquid crystal having a selective reflection region and a quarter wavelength plate, and a substrate Examples thereof include a polarizing element provided with a fine wire grid. In order to obtain the effect of the present invention more effectively, a hydrophilic polymer such as a polyvinyl alcohol film containing a dichroic dye such as a dye or a polyvalent iodine ion, which has excellent polarization characteristics as a polarizing element. It is preferable to use a polarizing element obtained by uniaxially stretching a film, or a polarizing element obtained by forming a polyene structure by dehydration with an acid before and after uniaxial stretching of a polyvinyl alcohol film.

  The polarizing element can be produced by a conventional method. For example, in the case of a polarizing element comprising a polyvinyl alcohol film containing a dichroic dye such as a dye and polyvalent iodine ions, first, the polyvinyl alcohol film After being swelled with warm water or the like, it is immersed in a dyeing tank in which a dichroic dye is dissolved, the film is dyed, and then stretched uniaxially in a tank containing a crosslinking agent such as boric acid or borax and dried. The polarizing element can be obtained. The performance of the polarizing element can be adjusted by the dichroism of the dichroic dye, the stretch ratio during stretching, and the like. Examples of the dye used for dyeing include an iodine-potassium iodide aqueous solution.

  The dye-based polarizing element of the present invention is a polarizing element produced by using a dye among dyes. Examples of the dye are described in “Application of functional dyes” (supervised by Masahiro Irie, CMMC Publishing) pages 98-100. An azo compound of Eye. direct. Yellow 12, sea. Eye. direct. Yellow 28, Sea. Eye. direct. Yellow 44, Sea. Eye. direct. Orange 26, Sea. Eye. direct. Orange 39, sea. Eye. direct. Orange 107, sea. Eye. direct. Red 2, sea. Eye. direct. Red 31, sea. Eye. direct. Red 79, Sea. Eye. direct. Red 81, Sea. Eye. direct. Red 247, Sea. Eye. direct. Green 80, Sea. Eye. direct. Green 59, and JP 2001-33627, JP 2002-296417, JP 2003-215338, WO 2004/092822, JP 2001-0564112, JP 2001-027708, JP 11-218611, JP 11-218610. And organic dyes described in JP-A-60-156759. These dichroic dyes are free acids, alkali metal salts (for example, Na salt, K salt and Li salt), ammonium salts, salts of amines, or complex salts (for example, Cu complex, Ni complex and Co complex). Etc. As the polarizing element used in the projection type liquid crystal display device, a dye-based polarizing element or a polarizing element obtained by forming a polyene structure is preferably used.

  The polarizing plate of the present invention can be obtained by laminating the protective film on at least one side of the polarizing element, usually on both sides using the adhesive, and then drying. The drying conditions vary depending on the concentration of the adhesive used and the moisture permeability of the protective film, but it is preferable to carry out the drying at 25 to 100 ° C. for about 10 to 150 minutes. The polarizing plate of the present invention may be a protective film on at least one side, and may be a glass substrate or the like on the other side. Usually, it is a polarizing plate in which a protective film is adhered to both surfaces of the polarizing element with the adhesive.

  In the present specification, the term “dye-based polarizing plate” refers to a polarizing plate produced from a dye-based polarizing element.

  As the inorganic substrate used in the present invention, a quartz substrate, a sapphire substrate, or an inorganic glass is used. Examples of the inorganic glass include blue plate glass (soda lime glass containing iron), white plate glass (crawn glass) (containing no iron). Soda lime glass), alkali-free glass (borosilicate glass), titanium silicate glass, or quartz glass. The shape may be plate-like, and the surface may be flat, or the surface may be uneven or spherical so as to have a function such as a lens or a prism.

As described above, any laminate in which the film or / and the substrate are bonded to the cured layer of the composition of the present invention enters the laminate of the present invention, and the combination of the size of the object to be bonded and the configuration of the layers There is no particular limitation.
As a preferable laminate of the present invention, at least any two of a polarizing element, a polarizing plate, an inorganic glass, a quartz substrate, and a sapphire substrate, in particular, one is a polarizing element or a polarizing plate, and the other is an inorganic glass, a quartz substrate, and A laminate that is one selected from the group consisting of sapphire substrates can be given. Also, (1) a configuration including at least one polarizing element, one inorganic glass, and one crystal substrate or one sapphire substrate, for example, inorganic glass is attached to one side of the polarizing element, and a crystal substrate or sapphire substrate is attached to the other side. (2) a configuration including at least one polarizing element and two inorganic glasses, for example, a polarizing plate in which inorganic glass is pasted on both sides of the polarizing element, and (3) at least one polarizing element and crystal Two substrates, or a configuration including a quartz substrate and a sapphire substrate, for example, a polarizing plate in which a quartz substrate is bonded to one side of the polarizing element and a quartz substrate or sapphire substrate is bonded to the other side, or (4) one polarizing element And a configuration including two sapphire substrates, for example, a polarizing plate in which a sapphire substrate is bonded to both surfaces of a polarizing element, for example.
After laminating these laminates with the above-described method, that is, the polarizing element and the substrate with the adhesive composition of the present invention, the adhesive layer is irradiated with ultraviolet rays, The adhesive layer is preferably produced by a method of curing the adhesive layer.
In the production of the laminate of the present invention, the adhesive composition of the present invention is sandwiched between release films, and an adhesive layer (or film) previously sandwiched between the release films is formed. It is a preferable method to bond an adherend film or an adherend substrate (hereinafter also referred to as an adherend) using the adhesive layer (or film). In order to adhere the adherends using the adhesive layer (or film), the adhesive layer (or film) sandwiched between the release films is taken out and used as an adhesive film. Hold between adhesives and paste them together, or, as described above, peel off the release paper and transfer the adhesive layer (or film) to the adherend while sandwiching it with the adherend. And may be pasted together.

1 and 2 show examples of the laminate of the present invention. In FIG. 1, a glass plate 1 and a sapphire substrate 2 are bonded to a polarizing element 4 via an adhesive layer 3 made of the blend composition of the present invention. In FIG. 2, two quartz substrates 5 are bonded to the polarizing element 4 via an adhesive layer 3 made of the composition of the present invention.
The board | substrate or film bonded together to a polarizing element can be selected arbitrarily, and is not restrict | limited to the thing of FIG. 1 and FIG.

  The polarizing plate of the present invention obtained as described above is improved in conventional image unevenness and thermal durability, and at the same time, there is no peeling due to the bonding layer and no deterioration or breakage of the polarizing element. Therefore, it can be suitably used for an optical system of an image display device, and is particularly suitable as a polarizing plate for a liquid crystal display device. The laminate of the present invention using a dye-based polarizing element or a dye-based polarizing plate can be more suitably used as a polarizing plate for a projection type liquid crystal display device.

  The polarizing plate of the present invention can be disposed as a polarizing plate in the vicinity of the light valve of the projection type liquid crystal display device. 3, 4, and 5 are schematic views of the vicinity of the light valve when one polarizing plate of the present invention is disposed in the vicinity (either one or both of the front and rear) of the projection type liquid crystal display device of the present invention. showed that. The display light 6 passes through the polarizing plate 8 of the present invention, the liquid crystal light valve 7 and, if necessary, the conventional polarizing plate 9 and is used for the display optical system. In FIG. 3, one polarizing plate 8 of the present invention is arranged on the incident side of the liquid crystal light valve 7, and a conventional polarizing plate 9 is arranged on the emission side. In FIG. 4, a conventional polarizing plate 9 is arranged on the incident side of the liquid crystal light valve 7, and one polarizing plate 8 of the present invention is arranged on the emitting side. In FIG. 5, the polarizing plate 8 of the present invention is disposed on both the incident side and the emission side of the liquid crystal light valve 7. The structure in the vicinity of the light valve is not limited to FIGS. 3, 4, and 5. Further, the liquid crystal light valve and the polarizing plate may be in close contact with each other or may be arranged at a distance. The incident-side polarizing plate and the outgoing-side polarizing plate are arranged at angles at which the respective absorption axes are orthogonal or parallel. When the laminate of the present invention is a polarizing plate, as shown in FIG. 1 and FIG. 2, when the polarizing element has a quartz substrate or sapphire substrate on one side and an inorganic glass on the other side, It is preferable to arrange the sapphire substrate on the liquid crystal light valve side.

Also, two polarizing plates of the present invention, or a combination of the polarizing plate of the present invention and a conventional polarizing plate, a total of two polarizing plates may be continuously installed in the vicinity of the liquid crystal light valve of the projection type liquid crystal display device. it can. A schematic view of the vicinity of the incident side of the liquid crystal light valve is shown in FIGS. In FIG. 6, the display light 6 first passes through the polarizing plate 8 of the present invention, and then passes through the conventional polarizing plate 9. In FIG. 7, the display light 6 first passes through the conventional polarizing plate 9 and then passes through the polarizing plate 8 of the present invention. In FIG. 8, the polarizing plate 8 of the present invention is arranged on both of two continuous polarizing plates. The arrangement of the two continuous polarizing plates can be arranged not only on the incident side of the liquid crystal light valve but also on the emission side. The liquid crystal light valve, the polarizing plate, and the polarizing plate may be in close contact with each other or may be arranged at a distance. When two polarizing plates are continuously installed at a position away from the liquid crystal light valve, the polarizing plate of the present invention to be installed has a crystal substrate or a sapphire substrate on one side of the polarizing element and an inorganic glass on the other side. In this case, the polarizing plate of the present invention is preferably arranged such that the quartz substrate or the sapphire substrate is on the liquid crystal light valve side.
When the polarizing plate of the present invention is installed at a position close to the liquid crystal light valve, it is preferable that the polarizing plate of the present invention uses either a quartz substrate or a sapphire substrate on both surfaces of the polarizing element.

When the polarizing plate of the present invention is arranged in an image display device as described above, the image display quality of the image display device is high, and the durability of the polarizing plate used is also good. In particular, in the projection type liquid crystal display device of the present invention, unevenness of the projected image is improved. Further, in the polarizing plate of the present invention, the remaining reactive compound in the photocurable adhesive generated in the polarizing plate using the conventional photocurable adhesive does not accelerate the deterioration of the polarizing element. In addition, there is no problem that the adhesive layer is easily peeled off due to curing shrinkage caused by the conventional photocurable adhesive, and further, there is no problem that the polarizing element caused by the combination of the polarizing element and the inorganic substrate is broken. Further, the problem that the physical and thermal durability is extremely lowered, which occurs when an adhesive is used for bonding, does not occur. Therefore, in the polarizing plate of the present invention, various problems caused by the adhesion with the polarizing plate which has occurred conventionally are solved. As a result, projection image unevenness, which is a conventional problem, is improved, the quality of the display image is improved, and the lifetime of the polarizing plate is greatly extended. At the same time, in the polarizing plate in which the polarizing element of the present invention is directly bonded to the inorganic substrate, compared with the case where the inorganic substrate for heat dissipation is bonded to a normal polarizing plate having triacetyl cellulose as a protective plate, The number of processes and the number of members can be reduced.
Moreover, since the adhesive composition of this invention has a shape maintenance performance by the compounding effect of an adhesive, it can be processed into a sheet sandwiched between two release films. Since the sheet-like adhesive is easy to handle and cut, the range of choice of manufacturing method and production machine is widened, which can contribute to improvement in production efficiency and cost reduction.

  The content of the present invention will be specifically described below using reference examples and examples, but the present invention is not limited thereto.

Reference Example Synthesis Example of Adhesive 94 g of n-butyl acrylate, 1 g of 2-hydroxyethyl acrylate, 5 g of N, N-dimethylacrylamide were dissolved in 185 g of ethyl acetate, 0.05 g of azobisisobutyronitrile was added, Polymerization was performed at 70 ° C. for 5 hours to obtain an acrylic resin copolymer solution. The obtained acrylic copolymer had a weight average molecular weight of 1,100,000 as determined by gel permeation chromatography (GPC) in terms of polystyrene.
Next, ethyl acetate was added to the obtained copolymer solution to prepare a resin content of 22.5% by weight. Then, 0.01 part by weight of 3-glycidoxypropyltrimethoxysilane and 0.002 part by weight of dibutyltin didodecanoate were blended to obtain an acrylic pressure-sensitive adhesive used in the present invention.

Example 1
(1) 79% by weight of an acrylic pressure-sensitive adhesive having a resin content of 22.5% by weight obtained in the above Reference Example, and an isocyanate-based crosslinking agent (Coronate ^RTM HL manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.035 Parts by weight, 0.009 parts by weight of 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.), 0.002 parts by weight of dibutyltin dilaurate (manufactured by Junsei Chemical Co., Ltd.), 3 as an alkoxysilane having an acrylic group -17 parts by weight of acryloxypropyltrimethoxysilane (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by weight of diacrylate of bisphenol A (manufactured by Nippon Kayaku Co., Ltd.) as a bifunctional photopolymerizable compound, Irga as a photopolymerization initiator 2 parts by weight of Irgacure-184 (manufactured by Ciba Specialty Chemicals) and 2-butanone 2 parts by weight were mixed to obtain a blend composition of the present invention. Methyl ethyl ketone was added and mixed well for 1 hour so that the solid content of the obtained blended composition was 20 parts by weight, to obtain the blended composition of the present invention for an adhesive sheet.
(2) Using a coating machine, the composition of the present invention obtained above was sandwiched between two release films (polyethylene terephthalate film) and molded into a sheet. The obtained sheet | seat was 20 micrometers in thickness, and was used as a double-sided adhesive sheet for laminated bodies.
(3) In order to produce the laminate (polarizing plate) of the present invention, a blue-channel dye-based polarizing element PBW (manufactured by Polatechno) and a green-channel dye-based polarizing element PGW (Polatechno) Prepared). On one side of each polarizing element, the double-sided adhesive sheet obtained above is bonded with a crawn glass board, and the other side is similarly bonded with a quartz substrate, and uncured A laminate (polarizing plate) of the present invention having an adhesive layer was prepared. A commercially available lami packer was used for pasting.
Using a high-pressure mercury lamp for UV irradiation twice, once for each side of the laminate of the present invention having an uncured adhesive layer, an integrated light quantity of 2500 mJ / cm ² (irradiation intensity of 20 mW / cm ² For 125 seconds) and photocured to obtain a laminate of the present invention. This laminate was evaluated by the evaluation method described after Table 1 below. The results are shown in Table 1.

Example 2
79% by weight of an acrylic pressure-sensitive adhesive having a resin content of 22.5% by weight obtained in the above Reference Example and a solid content of 0.035 parts by weight of an isocyanate-based crosslinking agent (Coronate HL manufactured by Nippon Polyurethane Industry Co., Ltd.), 3 -0.009 part by weight of glycidoxypropyltrimethoxysilane (KBE-403 manufactured by Shin-Etsu Chemical Co., Ltd.), 0.002 part by weight of dibutyltin dilaurate (manufactured by Junsei Chemical Co., Ltd.), 3-methacryloxypropyl as an alkoxysilane having an acrylic group 17 parts by weight of trimethoxysilane (KBE-503 manufactured by Shin-Etsu Chemical Co., Ltd.), 2 parts by weight of diacrylate of bisphenol A (manufactured by Nippon Kayaku Co., Ltd.) as a bifunctional photopolymerizable compound, Irgacure as a photopolymerization initiator -184 (Ciba Specialty Chemicals) 2 parts by weight and 2-butanone 32 parts by weight The composition of the present invention was obtained. Thereafter, a laminate of the present invention was produced in the same manner as in Example 1. This laminate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 3
An acrylic pressure-sensitive adhesive having a resin content of 22.5% by weight obtained in the above-mentioned Reference Example, a solid content of 76 parts by weight, an isocyanate-based crosslinking agent (Coronate HL manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.034 parts by weight, 0.009 part by weight of 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.), 0.002 part by weight of dibutyltin dilaurate (manufactured by Junsei Chemical Co., Ltd.), 3-acryloxy as an alkoxysilane having an acrylic group 17 parts by weight of propyltrimethoxysilane (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by weight of diacrylate of bisphenol A (manufactured by Nippon Kayaku Co., Ltd.) as a bifunctional photopolymerizable compound, as a trifunctional or higher functional photopolymerizable compound 3 parts by weight of tris (acryloxyethyl) isocyanurate (Aronix M-315 manufactured by Toagosei Co., Ltd.), photopolymerization initiator 2 parts by weight of Irgacure-184 (manufactured by Ciba Specialty Chemicals) and 30 parts by weight of 2-butanone were mixed to obtain a blended composition of the present invention. Thereafter, a laminate of the present invention was produced in the same manner as in Example 1. This laminate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 4
The acrylic pressure-sensitive adhesive having a resin content of 22.5% by weight obtained in the above-mentioned Reference Example was 87 parts by weight in terms of solid content, and 0.039 parts by weight of an isocyanate-based crosslinking agent (Coronate HL manufactured by Nippon Polyurethane Industry Co., Ltd.), 3 -0.01 part by weight of glycidoxypropyltrimethoxysilane (KBE-403 manufactured by Shin-Etsu Chemical Co., Ltd.), 0.002 part by weight of dibutyltin dilaurate (manufactured by Junsei Chemical Co., Ltd.), manufactured by Shin-Etsu Chemical Co., Ltd. as an alkoxysilane oligomer having an acrylic group 8 parts by weight of X-40-9271, 2 parts by weight of bisphenol A diacrylate (EF-053 manufactured by Nippon Kayaku Co., Ltd.) as a bifunctional photopolymerizable compound, urethane acrylate (FU-248 manufactured by Nippon Kayaku Co., Ltd.) 1 2 parts by weight, Irgacure-184 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator And 35 parts by weight of 2-butanone were mixed to obtain a blended composition of the present invention. Thereafter, a laminate of the present invention was produced in the same manner as in Example 1. This laminate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 5
The acrylic pressure-sensitive adhesive having a resin content of 22.5% by weight obtained in the above Reference Example was 93 parts by weight in terms of solid content, 0.042 parts by weight of an isocyanate-based crosslinking agent (Coronate HL manufactured by Nippon Polyurethane Industry Co., Ltd.), 3 -0.01 parts by weight of glycidoxypropyltrimethoxysilane (KBE-403 manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.002 parts by weight of dibutyltin dilaurate (manufactured by Junsei Chemical Co., Ltd.), Shin-Etsu Chemical Co., Ltd. as an alkoxysilane oligomer having an acrylic group 4 parts by weight of X-40-2655A manufactured by the manufacturer, 2 parts by weight of diacrylate of bisphenol A (EF-053 manufactured by Nippon Kayaku Co., Ltd.) as a bifunctional photopolymerizable compound, and 2,4,6-trimethyl as a photopolymerization initiator Benzoyldiphenylphosphine oxide (Lambson Fire Chemical Co., Ltd., trade name: Speed Cure TPO) 0.2 layer Parts, and 2-butanone 37 weight parts were mixed to obtain a blend composition of the present invention. Thereafter, a laminate of the present invention was produced in the same manner as in Example 1. This laminate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1
The acrylic pressure-sensitive adhesive having a resin content of 22.5% by weight obtained in the above Reference Example is 100 parts by weight in terms of solid content, and 0.045 parts by weight of an isocyanate-based crosslinking agent (Coronate HL manufactured by Nippon Polyurethane Industry Co., Ltd.), 3 -Glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.011 part by weight, dibutyltin dilaurate (manufactured by Junsei Chemical Co., Ltd.) 0.002 part by weight, and 40 parts by weight of 2-butanone were mixed and compared. A blending composition was obtained. Hereinafter, a comparative laminate was produced in the same manner as in Example 1 except that the photocuring treatment in Example 1 was not performed. This laminate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2
60 parts by weight of bisphenol A epoxy acrylate (R-310 manufactured by Nippon Kayaku) as a photopolymerizable compound, 20 parts by weight of urethane acrylate (UX-3204 manufactured by Nippon Kayaku) made of polyester diol and hexamethylene diisocyanate, 2- A photopolymerizable composition comprising 17 parts by weight of hydroxyethyl methacrylate and 3 parts by weight of Irgacure-184 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerizable compound is mixed with the present adhesive for adhesive sheets. The laminated body was produced by operation similar to Example 1 except using it for bonding instead of an adhesive compounding composition. This laminate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 3
As a protective plate, using a triacetyl cellulose film with a film thickness of 80 μm (Fuji Photo Film Co., Ltd., trade name: TD-80U) with one surface treated with alkali, on the surface of the two protective films treated with alkali, A 4% by weight aqueous solution of PVA glue (manufactured by Nippon Synthetic Chemical Co., Ltd., Gohsenol NH-26) was applied to obtain two protective films with glue on one side. A dye-type polarizing element (manufactured by Polatechno Co., Ltd.) obtained by stretching a polyvinyl alcohol-based resin film adsorbed with a dichroic dye is sandwiched between the two glue-coated protective films obtained above. Then, protective films were bonded to both surfaces of the polarizing element. Subsequently, by heating at 70 ° C. for 10 minutes and drying, polarizing plates for comparative blue channel and green channel were obtained.

  The evaluation results of the laminates and polarizing plates prepared in Examples 1 to 5 and Comparative Examples 1, 2, and 3 are shown in Table 1 below. The test and evaluation method are described after Table 1.

(1) Evaluation method of peeling / breaking at 90 ° C. A polarizing plate made of a laminate to be evaluated is put into a 90 ° C. oven and taken out after 1000 hours, and the peeling of the bonding layer and the breaking of the polarizing element film are visually observed. Observed.
(Double-circle): There is no peeling of a bonding layer and a fracture | rupture of a polarizing element film.
○: The edge of the bonded layer is slightly peeled off, and the polarizing element film is not broken.
X: Peeling of the bonding layer and breakage of the polarizing element film are observed.
(2) Blue channel light resistance evaluation A polarizing plate using a blue channel dye-based polarizing element made of a laminate to be evaluated is placed in the light path in the light resistance tester shown in FIG. 9 where a blue channel dichroic filter is installed for 600 hours. Arranged. Then, the transmittance | permeability at the time of arrange | positioning the polarizing plate of evaluation object and the standard polarizing plate of a spectrophotometer (JASCO Corporation V-7100) in cross nicol was evaluated. If there is deterioration, an increase in transmittance that is inherently low can be seen. Moreover, the transmittance | permeability at the time of arrange | positioning so that the absorption axis of the polarizing plate of evaluation object and the absorption axis of the standard polarizing plate of a spectrophotometer may become parallel was evaluated. When deterioration occurs, the transmittance decreases.
A: No increase in transmittance was observed when the polarizing plates were arranged in crossed Nicols, and no reduction in transmittance was observed when the polarizing plates were arranged in parallel.
X1: The transmittance when the polarizing plates were arranged in a crossed Nicol state was significantly increased, and when the polarizing plates were arranged in parallel, no decrease in the transmittance was observed.
X2: Although the raise of the transmittance | permeability at the time of arrange | positioning a polarizing plate in cross Nicol was not seen, the transmittance | permeability was reducing significantly when the polarizing plate was arrange | positioned in parallel.
(3) Green channel light resistance evaluation Blue channel light resistance, except that the laminate to be evaluated is a polarizing plate using a dye-type polarizing element for green channel, and a dichroic filter for green channel is installed in the light resistance tester. Evaluation was performed in the same manner as the evaluation.
A: No increase in transmittance was observed when the polarizing plates were arranged in crossed Nicols, and no reduction in transmittance was observed when the polarizing plates were arranged in parallel.
X: The transmittance when the polarizing plates were arranged in crossed Nicols was significantly increased, and no reduction in the transmittance was observed when the polarizing plates were arranged in parallel.

(4) Evaluation of unevenness of projection image One laminate produced was used for the blue channel exit side polarizing plate or the blue channel exit in the projection image unevenness tester shown in FIG. 10 using a commercially available projection type liquid crystal display device. By replacing either of the pre-polarizers, or both the blue channel exit-side polarizer and the blue channel exit pre-polarizer, the unevenness of the projected image was comparatively evaluated. In addition, the produced laminate is either the green channel exit side polarizing plate or the green channel exit pre-polarizing plate in the projection image unevenness testing machine, or the green channel exit side polarizing plate and the green channel exit. This was replaced with both of the pre-polarizers, and the unevenness of the projected image was compared and evaluated.
A: In both cases of the evaluation of the green channel and the evaluation of the blue channel, no unevenness of the projected image was observed.
X: Unevenness of the projected image was observed in the evaluation of the green channel, and slight unevenness of the projection image was also observed in the evaluation of the blue channel.

By comparing Examples 1 to 3 and Comparative Examples 1 and 2, a laminate (in the above, a polarizing plate) obtained using an adhesive processed from the blend composition of the present invention is for a projection type liquid crystal display device. Not only has high durability in the light resistance test, but also a polarizing plate that uses a triacetyl cellulose film as a protective plate does not cause a sharp drop in transmittance. Even if it is affected by heat generated during mounting, the bonding layer does not peel off and the polarizing element film does not break. Therefore, it can be seen that a projection-type liquid crystal display device having both high-quality projected images and high reliability can be realized.

The adhesive composition of the present invention has a good initial adhesion to a bonding material when the substrate and film, particularly a translucent inorganic substrate and a polarizing element or polarizing plate are bonded, and adhesion after bonding. It has excellent performance and durability, and does not deteriorate a functional film laminated such as a polarizing element. Further, the adhesive composition is a sheet-like adhesive. It is easy to handle and cut, can be easily bonded, and is suitable for bonding various laminated films or laminates used in electronic devices. Contributes to improvement and reduction of processing costs. In addition, a laminate having an adhesive layer composed of a photocured layer of an adhesive composition is relatively small in volume expansion or the like with respect to the thermal load of the inorganic substrate even if a thermal load is applied during use. The synthetic resin film (for example, a polarizing element) bonded to the substrate does not break, and is suitable for use in an environment where a thermal load is applied such as a projection type liquid crystal display device. When the used image display device is used, a projected image with very high display quality with little display unevenness can be obtained.
Therefore, the adhesive composition of the present invention is suitable as an adhesive for a laminate of a substrate and a film used as an optical member as described above, and is very useful industrially. .

1: Glass plate 2: Sapphire plate 3: Adhesive layer 4: Polarizing element 5: Crystal substrate 6: Display light 7: Liquid crystal light valve 8: Polarizing plate made of the laminate of the present invention 9: Conventional polarizing plate 10: UHP lamp 11: integrator lens 12: PBS
13: Condenser lens 14: Dichroic filter for blue channel evaluation or dichroic filter for green channel evaluation 15: UV absorbing glass 16: Polarizing plate made of the laminate of the present invention 17: Heat absorbing plate 18: Dichroic mirror 19: Mirror 20: Projection lens 21: Projection light 22: Projection screen 23: Red light 24: Green light 25: Blue light 26: Liquid crystal cell 27: Polarizing plate 28: Pre-polarizing plate 29: Pre-polarizing plate (green channel emission side)
30: Polarizing plate (green channel exit side)
31: Pre-polarizing plate (blue channel emission side)
32: Polarizing plate (blue channel exit side)

Claims (16)

  (A) (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer (component a), (b) photopolymerizable compound (component b) and (c) photopolymerization initiator (component c) as the adhesive component An adhesive composition containing an alkoxysilane having a photopolymerizable group as a photopolymerizable compound.   The pressure-sensitive adhesive composition according to claim 1, wherein the photopolymerizable group is at least one group selected from the group consisting of a (meth) acryl group, a vinyl group, and an epoxy group.   The adhesive composition according to claim 2, wherein the alkoxysilane having a photopolymerizable group is a monomer or an oligomer obtained by condensation polymerization of 2 to 70 monomers.   The adhesive according to claim 1, wherein the content of the acrylamide monomer-derived component in the (meth) acrylic acid C1-C12 alkyl ester-acrylamide copolymer is 1 to 49% by weight based on the entire copolymer. Sex composition.   The pressure-sensitive adhesive composition according to claim 1, comprising both an alkoxysilane having a photopolymerizable group and a photopolymerizable compound having two or more photopolymerizable groups in one molecule as the photopolymerizable compound.   The adhesive composition according to claim 5, wherein the photopolymerizable compound having two or more photopolymerizable groups in one molecule is a di- or triacrylate compound.   The content of the alkoxysilane having a photopolymerizable group is 0.5 wt% to 60 wt% with respect to the total amount of the components a, b and c of the adhesive composition. An adhesive composition.   The content of the photopolymerizable compound having two or more photopolymerizable groups in one molecule is from 1% by weight to 30% by weight based on the total amount of the components a, b and c of the adhesive composition. The adhesive composition according to claim 5, wherein the composition is%.   A laminate in which at least two substrates or two films, or a film and a substrate are bonded together by a photocured material layer of the blend composition according to any one of claims 1 to 8.   10. The two substrates or the two films, or one of the film and the substrate is a polarizing element or a polarizing plate, and the other is one selected from the group consisting of an inorganic glass plate, a quartz substrate and a sapphire substrate. The laminated body as described in.   The laminate according to claim 10, wherein the polarizing element or polarizing plate is a dye-based polarizing element or a dye-based polarizing plate.   The laminate according to claim 9 or 10, wherein the film is an organic film selected from the group consisting of a cellulose film, a polyvinyl alcohol film, a polyester film, a cycloolefin film, a polyethylene terephthalate film, and an acrylic film. body.   The image display apparatus which used the laminated body of Claim 9 or 10 for the optical system.   11. A projection type liquid crystal display device in which the laminate according to claim 9 or 10 is disposed on either or both of a light incident side and a light emitting side of a liquid crystal light valve.   At least two substrates or two films, or a film and a substrate are bonded to each other with the adhesive composition according to claim 1, and then, the adhesive composition is irradiated with ultraviolet rays. The method for producing a laminate according to claim 9 or 10, wherein the layer is cured.    2. The adhesive composition according to claim 1, wherein the adhesive composition contains an organic solvent, and the amount of the organic solvent is 1 to 10 times the total amount of the component a, component b, and component c according to claim 1. An adhesive composition.

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