JP2006124528A - Pressure-sensitive adhesive laminated product and liquid crystal cell member using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive laminated product capable of easily removing air which is formed on an adhesion interface, when adhered to a liquid crystal cell glass member, capable of being prevented from floating, nor peeling off, even when left under a high-temperature and high-humidity condition after adhered, and capable of preventing deterioration in optical characteristics, such as a transmission rate of light and phase difference (a retardation value: a product of a refractive index in birefringence and a thickness of a film), and to provide a liquid crystal cell member using the same. <P>SOLUTION: This pressure-sensitive adhesive laminated product is given by sequentially laminating a release sheet, a specified acrylic pressure-sensitive adhesive layer, a specified urethane-based pressure-sensitive adhesive layer, and an optical film. The liquid crystal cell member is given by sequentially laminating the liquid crystal cell glass member, the specified acrylic pressure-sensitive adhesive layer, the specified urethane-based pressure-sensitive adhesive layer, and the optical film. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a pressure-sensitive adhesive laminate comprising an acrylic pressure-sensitive adhesive layer and a urethane-based pressure-sensitive adhesive layer as essential constituent layers. More specifically, the present invention maintains excellent adhesiveness even under conditions of high temperature and high humidity, and further a liquid crystal cell. The present invention relates to a pressure-sensitive adhesive laminate that is less likely to cause deterioration in optical properties when used in a member for use.

  In the liquid crystal display element, liquid crystal is sealed between two substrates on which electrodes are arranged. A polarizing plate is further laminated with an adhesive or a polarizing plate and a retardation plate are laminated with an adhesive on the surface of the two substrates located outside the display device. Or

  A polarizing plate used in a liquid crystal display element has poor dimensional stability due to its material characteristics, and expands and contracts under heat or wet heat conditions to greatly change dimensions. For this reason, there are problems such as foaming of the pressure-sensitive adhesive layer under such conditions, floating of the polarizing plate from the liquid crystal cell, and peeling.

The adhesive for sticking an optical film to the board | substrate of a liquid crystal display element is disclosed by patent documents 1-3.
For example, Patent Document 1 uses an acrylic polymer having a specific functional group concentration such as a carboxyl group and a hydroxyl group of 5 × 1/10 ⁴ mol / g or less as a base polymer, and an isocyanate compound, an epoxy compound, or the like. There is disclosed a pressure-sensitive adhesive obtained by using as a crosslinking agent.
However, liquid crystal display devices have been increasing in performance and size in recent years, and conventional acrylic pressure-sensitive adhesives have not been able to adequately meet the strict requirements for moisture and heat resistance (maintaining optical properties and free of peeling / peeling). (Patent Document: JP-A-10-042991).

Patent Document 2: Japanese Patent Application Laid-Open No. 2003-292928 discloses that when a pressure-sensitive adhesive containing a specific urethane resin is used, a high-temperature and high-humidity atmosphere is obtained without causing blistering, floating or peeling even under high-temperature and high-humidity conditions. It is disclosed that the optical function can be maintained even when placed.
However, although the adhesive containing urethane resin has higher optical function maintenance characteristics than acrylic adhesives, its elastic modulus is high, so bubbles that have entered between the adhesive and the adherend during the bonding process. However, there is a problem of so-called poor air escape, which is difficult to remove compared to acrylic adhesives.

Further, Patent Document 3: Japanese Patent Application Laid-Open No. 2001-311062 discloses an adhesive sheet in which a polarizing plate, an acrylic adhesive layer having a high relaxation elastic modulus, an acrylic adhesive layer having a low relaxation elastic modulus, and a release sheet are sequentially laminated. It is disclosed. That is, in Patent Document 3, when the polarizing plate is contracted, an adhesive layer having a high relaxation elastic modulus ensures adhesion to the polarizing plate, prevents peeling, and an acrylic pressure-sensitive adhesive having a low relaxation elastic modulus. It is described that the stress caused by the contraction of the polarizing plate can be relaxed by the layer, and the local concentration of the residual stress can be prevented.
However, these pressure-sensitive adhesive layers are all composed of acrylic pressure-sensitive adhesives, and liquid crystal display devices are becoming increasingly high-performance and large-sized, and today, strict requirements for moisture and heat resistance (maintaining optical properties, floating / peeling off) I couldn't fully respond to that.
Japanese Patent Laid-Open No. 10-44291 JP 2003-292928 A Japanese Patent Laid-Open No. 2001-311062

  The present invention can easily remove the air generated at the adhesion interface when adhering to the glass member for a liquid crystal cell. After adhering, even if it is placed under high temperature and high humidity conditions, it does not float or peel off. An object of the present invention is to provide a pressure-sensitive adhesive laminate and a liquid crystal cell member using the same, in which optical properties such as transmittance and retardation (retardation value: product of birefringent refractive index and film thickness) do not deteriorate.

  As a result of intensive studies, the present inventors have used a pressure-sensitive adhesive laminate comprising an acrylic pressure-sensitive adhesive layer and a urethane-based pressure-sensitive adhesive layer as essential constituent layers, so that blisters, floats and peels even under high temperature and high humidity conditions. The present invention has been completed by finding that it has excellent optical function maintaining characteristics even when placed in a high-temperature and high-humidity atmosphere, and can overcome the poor air release during bonding of urethane-based adhesives.

  That is, the present invention relates to a pressure-sensitive adhesive laminate having an acrylic pressure-sensitive adhesive layer and a urethane pressure-sensitive adhesive layer as essential constituent layers.

  The present invention also relates to the pressure-sensitive adhesive laminate according to the above invention, wherein a peelable sheet is further laminated on at least one surface of both the pressure-sensitive adhesive layer of the acrylic pressure-sensitive adhesive layer and the urethane pressure-sensitive adhesive layer.

  Furthermore, the present invention relates to the pressure-sensitive adhesive laminate according to the above invention, wherein a peelable sheet, an acrylic pressure-sensitive adhesive layer, a urethane pressure-sensitive adhesive layer, and an optical film are sequentially laminated.

The acrylic pressure-sensitive adhesive layer comprises 100 parts by weight of a copolymer (A) having a weight average molecular weight of 1,000,000 to 2,000,000, which is obtained by radical copolymerization of the following monomers (a) and (b): 20 to 100 parts by weight of a copolymer (B) having a weight average molecular weight of 10,000 or more and 100,000 or less obtained by radical copolymerization of the bodies (c) and (d), and the copolymer (A) and / or the copolymer The above invention, characterized in that it is formed from an acrylic pressure-sensitive adhesive containing 0.003 to 3 parts by weight of a polyfunctional compound (C) having at least two reactive functional groups capable of reacting with the polymer (B). It is related with the adhesion laminated body in any one of these.
(a) a monomer having a reactive functional group and an ethylenically unsaturated double bond
(b) Other monomer having an ethylenically unsaturated double bond copolymerizable with (a) above
(c) Monomer having a carboxyl group and an ethylenically unsaturated double bond
(d) Other monomer having an ethylenically unsaturated double bond copolymerizable with the above (c)

  Further, the acrylic pressure-sensitive adhesive comprises a copolymer (B) obtained by radical copolymerization of the monomers (c) and (d) in the presence of the copolymer (A), and a polyfunctional compound (C). It contains about the adhesion laminated body as described in the said invention characterized by containing.

  The urethane-based pressure-sensitive adhesive layer is formed of a urethane-based pressure-sensitive adhesive containing a polyurethane (D) having a hydroxyl group and a polyisocyanate compound (E), and relates to the pressure-sensitive adhesive laminate according to any one of the above inventions.

Moreover, it is related with the adhesion laminated body as described in the said invention characterized by the amount of hydroxyl groups of the polyurethane (D) which has a hydroxyl group being 1 * 10 < ^-5 > ^-1 * 10 < ^-3 > (mol / g).

  Further, the polyurethane group (D) having a hydroxyl group is converted into an isocyanate group-containing urethane prepolymer (D1) obtained by reacting a polyol (d1) and a polyisocyanate (d2) under conditions of excess isocyanate, and a polyamino compound having a hydroxyl group ( A polyurethane polyurea having a hydroxyl group obtained by reacting an isocyanate group-containing polyurethane polyurea (D3) obtained by reacting D2) with an excess of isocyanate and a compound having an amino group and a hydroxyl group (D4). It relates to the pressure-sensitive adhesive laminate according to any one of the above inventions.

  Furthermore, the polyamino compound (D2) having a hydroxyl group is a compound obtained by Michael addition reaction of a polyamine (d3) and a compound (d4) having an unsaturated double bond and a hydroxyl group. It is related with the adhesion laminated body.

  The present invention also relates to a liquid crystal cell member in which a glass member for a liquid crystal cell, an acrylic pressure-sensitive adhesive layer, a urethane pressure-sensitive adhesive layer, and an optical film are sequentially laminated.

  According to the present invention, it is possible to obtain a pressure-sensitive adhesive laminate that has good air escape during the bonding and has excellent adhesiveness even when placed in a high-temperature and high-humidity atmosphere, and can maintain optical properties. Became.

[Adhesive laminate]
The pressure-sensitive adhesive laminate of the present invention will be described.
The pressure-sensitive adhesive laminate of the present invention essentially comprises two layers, an acrylic pressure-sensitive adhesive layer and a urethane pressure-sensitive adhesive layer, and preferably has a peelable sheet laminated on at least one surface of both layers. .
<Releasable sheet>
The peelable sheet used in the pressure-sensitive adhesive laminate of the present invention is also called a separator, and conventionally known ones can be used. For example, using a plastic film or paper made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate and the like, and having a peelable coat layer (silicone layer) formed on this substrate is used. it can.

  It can also be set as what is called a "double-sided adhesive laminated body" by which the 2nd peelable sheet is laminated | stacked on the surface which has not laminated | stacked the 1st peelable sheet. Or it can also be set as the so-called "single-sided adhesive laminated body" by which a non-peelable base material is laminated | stacked on the adhesive layer which has not laminated | stacked the 1st peelable sheet.

<Non-peelable substrate>
Non-peelable substrates used in the pressure-sensitive adhesive laminate of the present invention include so-called plate-like and film-like materials such as paper, metal plates, synthetic resin films, glass plates, rod-like materials, and other various shapes. Things. Moreover, various base materials can also be used independently, and the thing in the multilayer state formed by laminating | stacking a several thing can also be used.
Examples of the metal plate include a stainless steel plate, an aluminum plate, a steel plate, and a copper plate.
Examples of the synthetic resin film include synthetic resin films such as a polyethylene film and a polypropylene film.
As the non-peelable substrate used in the pressure-sensitive adhesive laminate of the present invention, a so-called optical film having optical properties such as a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film is preferable.
In the pressure-sensitive adhesive laminate of the present invention, one obtained by laminating a peelable sheet on one side and an optical film on the other side is also referred to as “optical film pressure-sensitive adhesive sheet” hereinafter.

<Optical film adhesive sheet>
In the case of such an optical film pressure-sensitive adhesive sheet, it is preferable that the urethane pressure-sensitive adhesive layer is located on the optical film side and the acrylic pressure-sensitive adhesive layer is located on the peelable sheet side.
In the case of an optical film that has poor dimensional stability and expands and contracts under wet heat conditions, such as a polarizing film, and the dimensions change greatly, the urethane adhesive layer suppresses the expansion and contraction and prevents the deterioration of optical properties Because there is.
By the way, the peelable sheet is peeled off, and the pressure-sensitive adhesive layer that appears is attached to the adherend, and air is generally involved in the sticking interface of the single-sided adhesive laminate to be used. As compared with the acrylic pressure-sensitive adhesive layer, the urethane-based pressure-sensitive adhesive layer retains the entrained air without disappearing over time. Therefore, it is preferable that the acrylic pressure-sensitive adhesive layer is located on the side where the optical film pressure-sensitive adhesive sheet is adhered to the adherend, that is, on the peelable sheet side.

Such an optical film adhesive sheet can be obtained by various methods as described below.
(1) Apply urethane adhesive to the optical film to form a urethane adhesive layer, apply acrylic resin adhesive on the urethane adhesive layer, and form an acrylic adhesive layer. A peelable sheet is laminated on the acrylic pressure-sensitive adhesive layer.
(2) Apply an acrylic pressure-sensitive adhesive to the peelable sheet to form an acrylic pressure-sensitive adhesive layer, and separately apply a urethane pressure-sensitive adhesive to the peelable sheet to form a urethane pressure-sensitive adhesive layer. The agent layer is laminated to obtain a double-sided pressure-sensitive adhesive laminate. Next, the peelable sheet on one side of the obtained double-sided pressure-sensitive adhesive laminate, preferably the peelable sheet on the urethane pressure-sensitive adhesive layer side, is peeled off, and an optical film is laminated on the urethane-based pressure-sensitive adhesive layer.
(3) An acrylic resin adhesive is applied on the peelable sheet, an acrylic adhesive layer is formed, a urethane adhesive is applied on the acrylic adhesive layer, and a urethane adhesive layer is formed. And forming an optical film on the urethane-based pressure-sensitive adhesive layer.
Each pressure-sensitive adhesive is applied by an arbitrary method such as a bar coating method, a roll coating method, a gravure coating method, or an air knife coating method.

  Although it does not specifically limit about the thickness of the whole adhesion laminated body of this invention, When sticking to the glass substrate for liquid crystal cells so that it may mention later, it is preferable to set it as about 2-300 micrometers, and 5 micrometers-100 micrometers. More preferably, it is more preferably 7 μm to 60 μm.

The thickness of each pressure-sensitive adhesive layer is not particularly limited, but the acrylic pressure-sensitive adhesive layer is preferably about 1 μm to 150 μm, more preferably 3 μm to 50 μm, and further preferably 7 μm to 30 μm. preferable. The urethane pressure-sensitive adhesive layer is preferably about 1 μm to 150 μm, more preferably 3 μm to 50 μm, and even more preferably 7 μm to 30 μm. In such a range, the above effect is more effectively exhibited.
The thickness ratio of each pressure-sensitive adhesive layer is preferably urethane pressure-sensitive adhesive layer / acrylic pressure-sensitive adhesive layer = 1/10 to 10/1, more preferably 1/5 to 5/1, and 1/3. ~ 3/1 is more preferred. That is, if the urethane pressure-sensitive adhesive layer / acrylic pressure-sensitive adhesive layer is less than 1/10, the urethane pressure-sensitive adhesive layer is relatively thin, so that the physical properties of the urethane-based pressure-sensitive adhesive layer cannot be sufficiently exhibited. When the agent layer / acrylic pressure-sensitive adhesive layer exceeds 10/1, the acrylic pressure-sensitive adhesive layer is relatively thin, and the physical properties of the acrylic pressure-sensitive adhesive are not sufficiently exhibited.

<Acrylic adhesive layer>
The pressure-sensitive adhesive used for forming the acrylic pressure-sensitive adhesive layer used in the present invention is not particularly limited, but is mainly a (meth) acrylic acid ester that is an adhesive force developing component and a cohesive force (holding force) developing component. It is preferable to use a compound having a functional group capable of reacting with the functional group as a crosslinking agent, the main component being a copolymer obtained by copolymerizing a monomer and a monomer having a functional group responsible for intermolecular crosslinking. .
Examples of the main component of the acrylic pressure-sensitive adhesive include, for example, monomer components such as butyl acrylate and 2-ethylhexyl acrylate having a glass transition temperature (hereinafter referred to as Tg) of each homopolymer of −20 ° C. or lower, and a Tg of 20 Copolymerizes monomer components responsible for the development of cohesive strength (holding power) that can form homopolymers at or above ° C and monomer components having functional groups such as hydroxyl groups, tertiary amino groups, carboxyl groups, amide groups, and nitrile groups The copolymer obtained is preferable.
These copolymers are crosslinked with a crosslinking agent such as an isocyanate crosslinking agent, a chelate crosslinking agent, or an epoxy crosslinking agent as is generally known.

This will be described based on a specific example. For example, in the case of applications requiring excellent tackiness under more severe conditions such as high temperature and high humidity atmosphere, a weight average molecular weight of 100 obtained by radical copolymerization of the following monomers (a) and (b): A copolymer (B) having a weight average molecular weight of 10,000 to 100,000, obtained by radical copolymerization of 100 parts by weight of a copolymer (A) of 10,000 to 2,000,000 and the following monomers (c) and (d): 20 to 100 parts by weight, and 0.003 to 3 parts by weight of a polyfunctional compound (C) having at least two reactive functional groups capable of reacting with the copolymer (A) and / or the copolymer (B) It is preferable to use an acrylic pressure-sensitive adhesive containing a part, and further, a copolymer (B) obtained by radical copolymerization of the monomers (c) and (d) in the presence of the copolymer (A), Acrylic pressure-sensitive adhesive containing a polyfunctional compound (C) It is more preferable to use.
(a) a monomer having a reactive functional group and an ethylenically unsaturated double bond
(b) Other monomer having an ethylenically unsaturated double bond copolymerizable with (a) above
(c) Monomer having a carboxyl group and an ethylenically unsaturated double bond
(d) Other monomer having an ethylenically unsaturated double bond copolymerizable with the above (c)

  The polymer (A) contained in the acrylic pressure-sensitive adhesive contains a monomer (a) having a reactive functional group and an ethylenically unsaturated double bond, and another ethylenic copolymer copolymerizable with (a). It is a copolymer obtained by radical copolymerization of the monomer (b) having a saturated double bond. Examples of the reactive functional group include a carboxyl group, a hydroxyl group, an amino group, an amide group, a maleimide group, an itaconimide group, a succinimide group, and an epoxy group. As the monomer (a) and the monomer (b), a (meth) acrylic monomer or a vinyl monomer is preferably used.

  Specific examples of the monomer (a) having a carboxyl group include (meth) acrylic acid, β-carboxyethyl acrylate, itaconic acid, crotonic acid, fumaric acid, fumaric anhydride, maleic acid, maleic anhydride, maleic acid Examples include butyl. Specific examples of the monomer (a) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylhexyl) -methyl acrylate, chloro-2-hydroxypropyl (meth) acrylate, Examples include diethylene glycol mono (meth) acrylate, caprolactone-modified (meth) acrylates, polyethylene glycol (meth) acrylates, and polypropylene glycol (meth) acrylates.

  Specific examples of the monomer (a) having an amino group include aminomethyl (meth), dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate and the like. Specific examples of the monomer (a) having an amide group include (meth) acrylamide, N-acryloylmorpholine, N-substituted (meth) acrylamide, N-vinylpyrrolidone and the like.

  Specific examples of the monomer (a) having a maleimide group include N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide and the like.

  Specific examples of the monomer (a) having an itacimide group include N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N- Examples include cyclohexyl leuconconimide and N-lauryl itaconimide.

  Specific examples of the monomer (a) having a succinimide group include N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxy. Examples include octamethylene succinimide.

  Specific examples of the monomer (a) having an epoxy group include glycidyl (meth) acrylate.

  These monomers can be used alone or in combination. The copolymerization ratio of the monomer (a) constituting the copolymer (A) is preferably 0.1 to 15% by weight based on the total amount of the monomers. When the copolymerization ratio is less than 0.1% by weight, the cohesive force of the pressure-sensitive adhesive is reduced, and the pressure-sensitive adhesive may foam or float off in a heating environment. On the other hand, when the content is more than 15% by weight, the adhesive strength of the adhesive may decrease.

  Specific examples of the monomer (b) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, iso-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl ( Examples include meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and phenoxyethyl (meth) acrylate. Moreover, aromatic vinyl monomers, such as styrene, methyl styrene, vinyl toluene, vinyl acetate, (meth) acrylonitrile, etc. are mentioned.

  The copolymerization ratio of the monomer (b) constituting the copolymer (A) is preferably 85 to 99.9% by weight based on the total amount of the monomers. When the copolymerization ratio is less than 85% by weight, the adhesion to the optical film or the glass member for liquid crystal cell is lowered. On the other hand, when the content is more than 99.9% by weight, the content of the monomer (a) having a reactive functional group is decreased, the cohesive force of the pressure-sensitive adhesive is reduced, and the pressure-sensitive adhesive foams or floats in a heating environment. Haggare may occur.

The copolymer (A) can be produced by any known method.
For example, the copolymer (A) is prepared by a method such as bulk polymerization or solution polymerization, preferably 0.001 to 1 part by weight of polymerization initiator, preferably solution weight, with respect to 100 parts by weight of the total amount of monomers. Synthesized by law. As the polymerization initiator, an azo compound or an organic peroxide is used, and two or more polymerization initiators may be used in combination. In the case of solution polymerization, as a polymerization solvent, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone, or the like is used. Two or more kinds of polymerization solvents may be mixed and used.

  Among the polymerization initiators, examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1- Carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2- Methyl propionate), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazoline) -2-yl) propane] and the like.

  Examples of the organic peroxide include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di (2-ethoxyethyl). Examples thereof include peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.

  The weight average molecular weight of the copolymer (A) needs to be 1 million or more and 2 million or less, and preferably 1.2 million or more and 1.8 million or less. The copolymer (A) having a weight average molecular weight of less than 1 million is insufficient in cohesive force of the pressure-sensitive adhesive even if it is used after crosslinking, and foaming or floating peeling occurs. On the other hand, when the weight average molecular weight is larger than 2 million, the viscosity of the pressure-sensitive adhesive becomes high and workability such as coating is inferior. In addition, the weight average molecular weight of the copolymer (A) was measured by gel permeation chromatography (GPC) by sampling a part of the reaction solution before starting the polymerization of the copolymer (B). calculate.

  The copolymer (B) contained in the acrylic pressure-sensitive adhesive contains other ethylenically unsaturated doubler copolymerizable with the monomers (c) and (c) having a carboxyl group and an ethylenically unsaturated double bond. It is a copolymer having a weight average molecular weight of 10,000 or more and 100,000 or less obtained by radical copolymerization of a monomer (d) having a bond. A copolymer (B) having a lower molecular weight than the copolymer (A) obtained by radical copolymerization of the monomer (c) and the monomer (d) in the presence of the copolymer (A) is an adhesive. If it is contained, the adhesive will not foam or peel off even under heat or wet heat conditions.

  As the monomer (c) and the monomer (d), (meth) acrylic monomers and vinyl monomers are preferably used. Specific examples of the monomer (c) include (meth) acrylic acid, β-carboxyethyl acrylate, itaconic acid, crotonic acid, fumaric acid, fumaric anhydride, maleic acid, maleic anhydride, butyl maleate and the like. It is done. These monomers can be used alone or in combination. The copolymerization ratio of the monomer (c) constituting the copolymer (B) is 0.1 to 50% by weight based on the total amount of the monomer (c) and the monomer (d). It is preferably 0.5 to 30% by weight.

  Further, when the monomers (c) and (d) are subjected to radical copolymerization in the presence of the copolymer (A), the monomer (d) may be a monomer constituting the copolymer (A) ( Among a), a monomer (a) having a reactive functional group other than a carboxyl group, and a monomer (b) can also be used. The copolymer (B) is a monomer having a carboxyl group and an ethylenically unsaturated double bond (c) and another monomer having an ethylenically unsaturated double bond that can be copolymerized with (c) ( d) can be produced by radical copolymerization in the same manner as the copolymer (A). The copolymer (B) is a residual monomer after radical copolymerization of the monomer (a) and the monomer (b) at a conversion rate of 50 to 90% to polymerize the copolymer (A). It is preferable to produce the product and the monomer (c) by radical copolymerization in the presence of the copolymer (A).

Moreover, it is preferable that the monomer and monomer (c) which remain | survive at the time of superposition | polymerization of a copolymer (A) are radically copolymerized by 70-100% of conversion. Here, the conversion rate is a value obtained by dividing the weight of the copolymer obtained by polymerizing the monomer by the total weight of the monomers used as raw materials.
By polymerizing the copolymer (A) and the copolymer (B) at the above conversion rate, the copolymer (B) is in the range of 20 to 100 parts by weight with respect to 100 parts by weight of the copolymer (A). It becomes easy to fit in.

  The copolymer (B) is preferably synthesized by a solution polymerization method, and is about 5 to 50 times the polymerization initiator at the time of synthesis of the polymer (A), that is, with respect to a total of 100 parts by weight of monomers. It is preferable to use 0.005 to 50 parts by weight of a polymerization initiator. In synthesizing the copolymer (B), a mercaptan such as lauryl mercaptan or n-dodecyl mercaptan, or a chain transfer agent such as α-methylstyrene dimer or limonene may be used.

  The weight average molecular weight of the copolymer (B) needs to be 10,000 or more and 100,000 or less, and more preferably 20,000 or more and 50,000 or less. When the copolymer (B) having a weight average molecular weight of less than 10,000 is used, the cohesive force is insufficient and foaming or floating peeling is likely to occur. Further, when the copolymer (B) having a weight average molecular weight exceeding 100,000 is used, the adhesion with the adherend is not sufficient. Here, the weight average molecular weight of the copolymer (B) is determined by GPC measurement of a mixture of the copolymer (A) and the copolymer (B), and the obtained GPC spectrum and the copolymer ( It is calculated from the difference spectrum from the GPC spectrum of A).

  Content of the copolymer (B) contained in an adhesive is 20-100 weight part with respect to 100 weight part of copolymers (A), Preferably it is 20-50 weight part. When the content of the copolymer (B) is less than 20 parts by weight, the adhesion with the adherend is hardly exhibited. Moreover, when content of a copolymer (B) exceeds 100 weight part, the cohesive force of an adhesive is insufficient and it is easy to produce foaming or floating peeling.

  The weight ratio of the copolymer (A) and the copolymer (B) is determined by the following method. That is, first, a predetermined amount of the solution sampled before starting the polymerization of the polymer (B) is put in a container of known weight and precisely weighed. The components are volatilized, the container in which only the copolymer (A) remains is precisely weighed, and the weight of the copolymer (A) contained in a certain amount of solution is calculated. Next, after the completion of the polymerization of the copolymer (B), a solution containing the copolymer (A) and the copolymer (B) is sampled, and the same method as when the weight of the copolymer (A) is calculated. Then, the weight of the copolymer (A) and the copolymer (B) contained in a certain amount of solution is calculated. Then, the weight of the copolymer (A) and the mixture of the copolymer (A) and the copolymer (B) contained in a certain amount of the solution is compared with the weight of the copolymer (A) and the copolymer contained in the same amount of the solution. By converting to the weight of the mixture of the copolymer (A) and the copolymer (B) and subtracting the copolymer (A) from the weight of the mixture of the copolymer (A) and the copolymer (B), The weight of the combined (B) is calculated.

  The polyfunctional compound (C) having at least two reactive functional groups capable of reacting with the copolymer (A) and / or the copolymer (B) contained in the acrylic pressure-sensitive adhesive is a copolymer (A). A compound having at least two, preferably 2 to 4 reactive functional groups that can react with a reactive functional group and / or a reactive functional group other than a carboxyl group or a carboxyl group that the copolymer (B) has is there. Examples of such polyfunctional compounds include isocyanate compounds, epoxy compounds, amine compounds, metal chelate compounds, aziridine compounds, and the like. In particular, isocyanate compounds, epoxy compounds, and aziridine compounds are preferred. Polyfunctional compounds can be used alone or in combination.

  Examples of isocyanate compounds include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane trisene. Polyisocyanate compounds such as isocyanate and polymethylene polyphenyl isocyanate, adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane, burettes and isocyanurates of these polyisocyanate compounds, and further these polyisocyanate compounds Known polyether polyols and polyesters Ether polyols, acrylic polyols, polybutadiene polyols, adducts, etc. and polyisoprene polyol and the like.

  Examples of epoxy compounds include bisphenol A-epichlorohydrin type epoxy resins, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) ) Cyclohexane, N, N, N ′, N′-tetraglycidylaminophenylmethane, triglycidyl and the like.

  Examples of the aziridine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridinecarboxite), Bisisophthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite), trimethylolpropane tri- β-aziridinylpropionate, tetramethylolmethane tri-β-aziridinylpropionate, tris-2,4,6- (1-aziridinyl) -1,3,5-triazine and the like can be mentioned.

  Content of a polyfunctional compound (C) is 0.003-3 weight part with respect to 100 weight part of said copolymers (A). When the content of the polyfunctional compound (C) is less than 0.003 parts by weight, the cohesive force of the pressure-sensitive adhesive is insufficient, and foaming or floating peeling is likely to occur. Moreover, when more than 3 weight part, cohesion force becomes strong too much and adhesiveness with a to-be-adhered body falls.

More preferably, the acrylic pressure-sensitive adhesive contains a silane coupling agent.
As silane coupling agents, vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyl Dimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyl Methoxysilane N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-merca DOO triethoxysilane, mercaptopropyl butyl trimethoxysilane γ- mercaptopropyl methyl dimethoxy silane, and the like.

  As for content of the silane coupling agent in an acrylic adhesive, 0.01-2 weight part is preferable with respect to 100 weight part of copolymers (A). If the amount is less than 0.01 parts by weight, the effect of improving the physical properties is poor. If the amount exceeds 2 parts by weight, the pressure-sensitive adhesive is not only expensive, but also causes floating peeling. Moreover, you may mix | blend a ultraviolet absorber, antioxidant, tackifying resin, a plasticizer, an antifoamer, and a leveling regulator with an adhesive.

The acrylic pressure-sensitive adhesive can be produced through the following steps (1) to (3).
(1) Monomers (a) and (a) having a reactive functional group and an ethylenically unsaturated double bond
And a step of polymerizing the copolymer (A) by radical copolymerization of another monomer (b) having an ethylenically unsaturated double bond that can be copolymerized with the compound at a conversion rate of 50 to 90%.
(2) A monomer having a carboxyl group and an ethylenically unsaturated double bond (c) and a monomer (d) having another ethylenically unsaturated double bond copolymerizable with (c) can be radically copolymerized. A step of synthesizing a copolymer (B) having a weight average molecular weight of 10,000 to 100,000, or a monomer, a carboxyl group, and an ethylenically unsaturated double remaining during the polymerization of the copolymer (A) A step of polymerizing the copolymer (B) by radical copolymerizing the monomer (c) having a bond in the presence of the copolymer (A) at a conversion rate of 70% to 100%.
(3) A step of adding a polyfunctional compound (C) having at least two reactive functional groups capable of reacting with the copolymer (A) and / or the copolymer (B).

[[Urethane adhesive]]
Next, the urethane pressure-sensitive adhesive used in the present invention will be described.
The urethane type adhesive in this invention contains the polyurethane (D) which has a hydroxyl group, and a polyisocyanate compound (E), and a urethane type adhesive layer is formed by reaction of both components.

[Polyurethane having a hydroxyl group (D)]
The polyurethane (D) having a hydroxyl group has a suitable cohesive force when the amount of hydroxyl group is in the range of 1 × 10 ⁻⁵ to 1 × 10 ⁻³ (mol / g), and functions as an adhesive for optical films. Is demonstrated.
Such a hydroxyl group-containing polyurethane (D) is an isocyanate group-containing polyurethane polyurea (D3) obtained by reacting an isocyanate group-containing urethane prepolymer (D1) with a hydroxyl group-containing polyamino compound (D2) under conditions of excess isocyanate. And a polyurethane urea having a hydroxyl group, which is obtained by reacting a compound (D4) having an amino group and a hydroxyl group.

<Isocyanate group-containing urethane prepolymer (D1)>
The isocyanate group-containing urethane prepolymer (D1), which is one of the raw materials constituting the polyurethane (D), is a compound obtained by reacting a polyol (d1) and a polyisocyanate (d2) under an isocyanate-excess condition.

  As the polyol (d1) used here, one or more of high molecular weight polyols, or bisphenols such as bisphenol A and bisphenol F, and alkylene oxides such as ethylene oxide and propylene oxide were added to bisphenols. Glycols and other polyols can also be used. Furthermore, compounds having two or more active hydrogen groups obtained by reaction of one or more of these with other compounds such as olefins and aromatic hydrocarbons can also be used.

  High molecular weight polyols are compounds having a repeating unit with a polymerization degree of 2 or more and having two hydroxyl groups, and examples thereof include polyester polyols, polyether polyols, and polycarbonate polyols.

Known polyester polyols can be used as the polyester polyols used in the present invention.
For example, there is a polyester polyol in which a polyol component and a dibasic acid component are subjected to a condensation reaction.
Among the polyols, diols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 3,3′-diene. Methylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, Examples of the polyol having three or more hydroxyl groups include glycerin, trimethylolpropane, and pentaerythritol.
Examples of the dibasic acid component include aliphatic or aromatic dibasic acids such as terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid.
Moreover, polyester polyol obtained by ring-opening polymerization of cyclic ester compounds such as lactones such as ε-caprolactone poly (β-methyl-γ-valerolactone) and polyvalerolactone, polycarbonate polyol, silicon polyol, and the like can be used.
The weight average molecular weight of the polyester polyols is preferably 500 to 5,000, more preferably 1,000 to 3,500.

Known polyether polyols can be used as the polyether polyols used in the present invention.
For example, by condensation of tetrahydrofuran, or a polymer, copolymer or graft copolymer of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, or hexanediol, methylhexanediol, heptanediol, octanediol, or a mixture thereof Those having two or more hydroxyl groups, such as polyether polyols and propoxylated or ethoxylated polyether polyols, can be used.
The weight average molecular weight of the polyether polyols is preferably 100 to 100,000, more preferably 500 to 25,000, and still more preferably 1,000 to 10,000 in order to facilitate the extraction of the side chain effect. It is.

  Examples of the polymerization initiator when polymerizing alkylene oxide include polypropylene glycol, ethylene glycol, glycerin, sorbitol, trimethylolpropane, trimethylolbutane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, and the like. A polyether polyol which is a trihydric or higher alcohol is also preferably used. Adducts of partially esterified polyhydric alcohols and polyether polyols can also be used. In this case, the polyether moiety may be a block polymer or a random polymer. The terminal to which the polyether polyol is added is a hydroxyl group, but may be partially an alkyloxy group or an aromatic hydrocarbonoxy group.

The polycarbonate polyol used in the present invention has a group represented by the following formula (1), and a known polycarbonate polyol can be used.
Formula (1)
— [— O—R ¹ —O—CO—] _m — (wherein R ¹ represents a divalent organic residue, and m represents an integer of 1 or more).

  Polycarbonate polyol is, for example, 1) Reaction of glycol or bisphenol with carbonate. 2) Obtained by a reaction in which phosgene is allowed to act on glycol or bisphenol in the presence of an alkali.

Specific examples of the carbonic acid ester used in the production method 1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

  Specific examples of the glycol component or bisphenol used in the production method 1) include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, and 2-methyl. -1,8-octanediol, 3,3′-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, 3,9-bis ( , 1-dimethyl-2-hydroxyethyl, 2,2,8,10-tetraoxospiro [5.5] undecane, bisphenols such as bisphenol A and bisphenol F, bisphenols and alkylenes such as ethylene oxide and propylene oxide Bisphenols to which oxides are added can also be used, etc. These compounds can be used as one kind or a mixture of two or more kinds.

  The glycol can also be used in the method 2) in which phosgene is allowed to act on glycol or bisphenol in the presence of an alkali.

  Specific examples of the polycarbonate polyol include Kuraray Polyol C series manufactured by Kuraray Co., Ltd.

  Among them, PMHC-1050, PMHC-2050, C-1090, C-2090, C-1065N, C-2065N, C-1015N, and C-2015N are preferable because they are flexible and excellent as a raw material for the pressure-sensitive adhesive.

  The weight average molecular weight of the polycarbonate polyol is preferably 500 to 5,000, more preferably 1,000 to 3,500. When the weight average molecular weight is less than 500, the resin becomes too hard when the urethane resin is synthesized, and becomes brittle. When the weight average molecular weight exceeds 5,000, the cohesive force of the urethane resin is insufficient.

  The polyol (d1) may be a urethane polyol having a terminal hydroxyl group by reacting the above polyether polyol and / or polyester polyol and / or polycarbonate polyol with the following polyisocyanate of less than the equivalent molar equivalent.

  Other polyols include ethylene glycol, diethylene glycol, triethylene glycol, butanediol, propanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, 3,9-bis (1,1-dimethyl-2 -Compounds having two hydroxyl groups such as hydroxyethyl 2,2,8,10-tetraoxospiro [5.5] undecane, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, methylglucoside, etc. Examples thereof include compounds having 3 or more hydroxyl groups.

<Polyisocyanate (d2)>
The polyisocyanate (d2) used in the present invention is for reacting the above-described polyol (d1) with an isocyanate group-excess condition to obtain an isocyanate group-containing urethane prepolymer (D1).
A conventionally well-known thing can be used as such polyisocyanate (d2), for example, aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, alicyclic polyisocyanate, etc. are mentioned.

  Aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-triisocyanate. Range isocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 " -Triphenylmethane triisocyanate etc. can be mentioned.

  Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate. 2,4,4-trimethylhexamethylene diisocyanate and the like.

  Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of alicyclic polyisocyanates include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl- Examples include 2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylene bis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane and the like.

  In addition, a trimethylolpropane adduct of the above polyisocyanate, a trimer having an isocyanurate ring, etc. can be used in combination. Polyphenylmethane polyisocyanate (PAPI), naphthylene diisocyanate, and these polyisocyanate modified products can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of polyol and diisocyanate can also be used as polyisocyanate (d2).

  As the polyisocyanate (d2) used in the present invention, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), xylylene diisocyanate, Use of a non-yellowing or hard yellowing polyisocyanate compound such as 4,4′-methylenebis (cyclohexyl isocyanate) (hydrogenated MDI) is preferred from the viewpoint of weather resistance.

<Catalyst (d5)>
When the urethane prepolymer (D1) is obtained from the polyol (d1) and the polyisocyanate (d2) under an excess of isocyanate groups, a known catalyst (d5) can be used. Examples thereof include tertiary amine compounds and organometallic compounds.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (DBU), and the like. In some cases, they can be used alone or in combination.

  Examples of organometallic compounds include tin compounds and non-tin compounds.

  Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, Examples include triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.

  Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate and butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate, 2- Examples include iron series such as iron ethylhexanoate and iron acetylacetonate, cobalt series such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc series such as zinc naphthenate and zinc 2-ethylhexanoate, and zirconium naphthenate. It is done.

  Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

  Catalysts such as the tertiary amine compounds and organometallic compounds can be used alone in some cases, but can also be used in combination. Especially when polyester diols and polyether diols are used in combination as polyol components, Use of dibutyltin dilaurate and tin 2-ethylhexanoate in combination is preferable because a uniform urethane prepolymer (D1) can be obtained.

  The organometallic compound catalyst used when synthesizing the urethane prepolymer (D1) remarkably accelerates the reaction when it further reacts with the amine described below. The reaction between an isocyanato group and an amino group is very fast from the beginning, but in the presence of an organometallic compound catalyst, the reaction may be further promoted and may be difficult to control. At this time, if a chelate compound is present, a chelate is formed with the organometallic compound catalyst, and the catalytic ability is adjusted to facilitate control of the reaction with the amine.

  Examples of the chelate compound include acetylacetone, dimethylglyoxime, oxine, dithizone, polyaminooxyacids such as ethylenediaminetetraacetic acid (EDTA), oxycarboxylic acids such as citric acid, and condensed phosphoric acid. Among the chelate compounds, acetylacetone is soluble in an organic solvent, has volatility, and is preferably easy to remove if necessary.

  In addition, the chelate compound remains in the polyurethane (D) having a hydroxyl group even after the reaction. The urethane-based pressure-sensitive adhesive used in the present invention contains a polyurethane (D) having a hydroxyl group and a polyisocyanate compound (E). The chelate compound can also adjust the reaction rate between the polyurethane (D) having a hydroxyl group and the polyisocyanate compound (E), and as a result, can provide an adhesive having excellent storage stability.

In the synthesis of the isocyanate group-containing urethane prepolymer (D1) used in the present invention, a known solvent is preferably used.
The use of a solvent serves to facilitate reaction control. Examples of the solvent used for such purpose include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, benzene, dioxane, acetonitrile, tetrahydrofuran, diglyme, dimethyl sulfoxide, N-methylpyrrolidone and the like. In view of the solubility of the isocyanate group-containing urethane prepolymer (D1), the boiling point of the solvent, etc., and the solubility of the polyamino compound (D2) having a hydroxyl group described later, ethyl acetate, toluene, methyl ethyl ketone, or a mixed solvent thereof is particularly preferable. The concentration in the reaction system when synthesizing the isocyanate group-containing urethane prepolymer (D1) when a solvent is used is preferably from 50 to 95%, more preferably from 60 to 90%, of the resin solid content. If it is too low, the reactivity is too low, which is not preferable.

The synthesis method of the isocyanate group-containing urethane prepolymer (D1) will be described more specifically.
Various methods can be used for the urethanization reaction in which the polyol (d1) and the polyisocyanate (d2) are reacted to form the urethane prepolymer (D1). A compound (f), (f) or a compound having 1) a reaction in the whole amount charged, and 2) a polyol (d1) and, if necessary, a group capable of reacting with at least one ionic functional group and an isocyanato group. The method is roughly divided into a method in which a solvent is charged into a flask and a polyisocyanate (d2) is added dropwise, and then a catalyst is added if necessary, but 2) is preferable when the reaction is precisely controlled. The reaction temperature for obtaining the urethane prepolymer (D1) is preferably 120 ° C. or lower. More preferably, it is 50-110 degreeC. When the temperature is higher than 110 ° C., it becomes difficult to control the reaction rate, and a urethane prepolymer having a predetermined molecular weight and structure cannot be obtained. The urethanization reaction is preferably performed at 50 to 110 ° C. for 1 to 20 hours in the presence of a catalyst.

The blending ratio of the polyol (d1) and the polyisocyanate (d2) is such that the molar equivalent of active hydrogen capable of reacting with the isocyanate group of the polyol (d1), the compounds (f) and (f ′) so that the isocyanate group remains at the terminal. For 1, it is necessary that the isocyanato group molar equivalent of polyisocyanate (d2) is greater than 1. The appropriate blending ratio greatly depends on the reactivity of the compound, the abundance ratio of the trivalent or higher compound, the use of the obtained resin, and the like. At the time of synthesizing a urethane prepolymer in which both ends are isocyanate, the equivalent ratio of the isocyanate group to the active hydrogen group of the hydroxyl group or the functional group capable of reacting with the isocyanate group is 1.01 to 4.00, preferably 1.40 to 3 Within the range of .00 is appropriate.

[Polyamino compound having hydroxyl group (D2)]
The polyamino compound (D2) having a hydroxyl group is used as a raw material for the purpose of urea modification of the isocyanate group-containing urethane prepolymer (D1).
That is, the polyamino compound (D2) having a hydroxyl group has at least two primary or secondary amino groups and a hydroxyl group. Those having a secondary amino group are preferred from the viewpoint of reactivity control. The polyamino compound (D2) having a hydroxyl group is preferably a Michael addition product of —NH ₂ and —C═C— as described later. Accordingly, the amino group of the polyamino compound (D2) having a hydroxyl group is preferably a secondary amino group, —NH—. This secondary amino group reacts with the isocyanate group of the isocyanate group-containing urethane prepolymer (D1) to form the isocyanate group-containing urethane urea polymer (D3). And by this urea modification | denaturation, the hydroxyl group derived from the polyamino compound (D2) which has a hydroxyl group can be introduce | transduced into the side chain of an isocyanate group containing urethane urea polymer (D3). The hydroxyl group of this side chain becomes a part of the hydroxyl group of the polyurethane (D) having a hydroxyl group as a so-called main agent of the urethane-based pressure-sensitive adhesive, and becomes a reaction point with the polyisocyanate compound (E) described later.

<Polyamine (d3)>
The polyamine (d3) used as a raw material for the polyamino compound (D2) having a hydroxyl group in the present invention is a compound having at least two primary or secondary amino groups. The amino group of the polyamine (d3) is preferably a primary amino group in that the reactivity of the Michael addition reaction with the compound (d4) having an unsaturated double bond and a hydroxyl group is high.

As the polyamine (d3) used in the present invention, a known one can be used. Specifically,
Ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, tolylenediamine, hydrazine, piperazine, etc. Aliphatic polyamines,
Examples thereof include aliphatic polyamines including alicyclic polyamines such as isophorone diamine and dicyclohexylmethane-4,4′-diamine, and aromatic polyamines such as phenylenediamine and xylylenediamine.
Furthermore, 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine , (2-hydroxypropylethylene) diamine, (di-2-hydroxypropylethylene) diamine and other diamines having a hydroxyl group in the molecule, dimer amine obtained by converting the carboxyl group of dimer acid to an amino group, and propoxyamine at both ends And polyoxyalkylene glycol diamines represented by the following formula (2) can also be used. H ₂ —NCH ₂ —CH ₂ —CH ₂ —O (C _n H _2n —O) _o —CH ₂ —CH ₂ —CH ₂ —NH ₂ (2) (in the formula (2), n is 2 to 4) Arbitrary integer, o represents any integer from 2 to 50.)
Among the polyamines (d3), isophorone diamine, 2,2,4-trimethylhexamethylene diamine, and hexamethylene diamine are preferable because of easy control of the reaction and excellent hygiene.

<Compound (d4) having unsaturated double bond and hydroxyl group>
In the present invention, the unsaturated double bond and the compound (d4) having a hydroxyl group, which are used as one of the raw materials of the polyamino compound (D2) having a hydroxyl group, have an amino group of the above-mentioned polyamine (d3) in the unsaturated double bond. Is used to add Michael. As a result of Michael addition, —NH ₂ (primary amino group) possessed by polyamine (d3) becomes —NH— (secondary amino group), and the resulting polyamino compound (D2) is unsaturated double It has a hydroxyl group derived from the compound (d4) having a bond and a hydroxyl group.

Moreover, when obtaining the polyamino compound (D2) which has a hydroxyl group, in addition to the compound (d4) which has a hydroxyl group in addition to the unsaturated double bond, the compound which has an unsaturated double bond and does not have a hydroxyl group It is preferable to use together.
Examples of the unsaturated compound (d4) having the above structure include (meth) acrylate compounds, fatty acid vinyl compounds, alkyl vinyl ether compounds, α-olefin compounds, vinyl compounds, ethynyl compounds, and the like. The unsaturated compound (d4) may have a functional group such as a hydroxyl group, an alkoxy group, a carboxyl group, an amide group, or a silanol group.

  Examples of (meth) acrylate compounds include alkyl (meth) acrylates and alkylene glycol (meth) acrylates.

  More specifically, as the alkyl-based (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) Acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadeci There are alkyl (meth) acrylates having 1 to 22 carbon atoms such as (meth) acrylate, icosyl (meth) acrylate, henecosyl (meth) acrylate, docosyl (meth) acrylate, etc. Examples thereof include an alkyl group-containing acrylate having a C 2-10 alkyl group, more preferably a C 2-8 alkyl group, or a corresponding methacrylate. When the carbon number is 23 or more, the Michael addition reaction is difficult to proceed.

  Examples of the alkylene glycol (meth) acrylate include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, and polyethylene glycol. Mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth), etc. Monoacrylate having a polyoxyalkylene chain or the corresponding monomethacrylate, methoxyethylene glycol (meth) acrylate, methoxydiethyl Glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (Meth) acrylate, n-pentoxytetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth) acrylate , Ethoxytetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol ( (Meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol ( (Meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, monoacrylate having an alkoxy group at the terminal and having a polyoxyalkylene chain or a corresponding monomethacrylate, such as phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate , Phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate Rate, phenoxy hexaethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, polyoxyalkylene acrylate or the corresponding methacrylates having a phenoxy or aryloxy group at the terminal such as phenoxy tetrapropylene glycol (meth) acrylate.

  Among the acrylates having the polyoxyalkylene chain or the corresponding methacrylates, the hydroxyl-terminated compound has a catalytic effect in the Michael addition reaction, and can be a crosslinking site when the curing agent (E) is used. Are preferably used.

  Carboxylic group-containing unsaturated compounds include maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (meth) Examples include acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and the like. I can do it.

  Examples of hydroxyl-containing unsaturated compounds other than those described above include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and 4-hydroxyvinylbenzene. And so on.

  Examples of the nitrogen-containing unsaturated compound include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, and N-propoxymethyl- (meth) acrylamide. , N-butoxymethyl- (meth) acrylamide, monoalkylol (meth) acrylamide such as N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl ( (Meth) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide, N, Acrylamide-type unsaturated compounds such as N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide, dialalkylol (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( Examples thereof include unsaturated compounds having a dialkylamino group such as (meth) acrylate methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene and the like.

  Further, other unsaturated compounds include perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2 -Perfluorooctylethyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) ) Acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate, etc. Perfluoroalkylalkyl (meth) acrylates having a kill group; perfluoroalkyl group-containing vinyl monomers such as perfluoroalkyls such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, and perfluorodecylethylene, and alkylenes , Vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane and other silanol group-containing vinyl compounds and derivatives thereof. A plurality can be used.

  Examples of the fatty acid vinyl compound include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, and vinyl stearate.

  Examples of the alkyl vinyl ether compound include butyl vinyl ether and ethyl vinyl ether. Examples of the α-olefin compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and the like.

  Examples of vinyl compounds include allyl compounds such as allyl acetate, allyl alcohol, allylbenzene, and allyl cyanide, vinyl cyanide, vinylcyclohexane, vinyl methyl ketone, styrene, α-methylstyrene, 2-methylstyrene, and chlorostyrene. Can be mentioned.

  Examples of the ethynyl compound include acetylene, ethynylbenzene, ethynyltoluene, 1-ethynyl-1-cyclohexanol and the like. These can be used alone or in combination of two or more.

<Michael addition reaction> Formation of polyamino compound (D2) having a hydroxyl group Michael addition between the above polyamine (d3) and a compound having an unsaturated double bond and a hydroxyl group (d4) and a compound having an unsaturated double bond The reaction will be described in detail.
The amino group of polyamine (d3) and 1 molar equivalent of active hydrogen of —NH ₂ react with 1 molar equivalent of unsaturated group of unsaturated compound (d4). Since the polyamine (d3) is easily Michael-added to the vinyl group or ethynyl group of the unsaturated compound (d4) having an electron-withdrawing group, a (meth) acrylic compound, particularly an acrylate compound is used as the compound (d4). preferable. In addition, when the acrylate compound and the corresponding methacrylate compound are compared, the acrylate compound is more preferable for the efficiency of the Michael addition reaction.

As a method for synthesizing the polyamino compound (D2) having a hydroxyl group, a known method relating to the Michael addition reaction can be used as it is.
For example, when the unsaturated compound is a (meth) acrylic compound, particularly an acrylate compound, the reaction proceeds at 10 to 100 ° C. under a catalyst such as alcohol as necessary. Although depending on the type of unsaturated compound used, a reaction temperature of 40 to 80 ° C. is preferred. If the reaction temperature is too high, an ester amide exchange reaction occurs, which is not preferable. In addition, when the unsaturated compound does not have an electron-withdrawing group, the reaction is possible in the presence of the metal catalyst. In this case, when the reaction is performed at 60 to 100 ° C. while heating in the presence of the catalyst, an appropriate reaction rate is obtained. It is preferable. The synthetic solvent may or may not be used, and the kind thereof is not particularly limited, but known solvents such as methyl ethyl ketone, toluene, acetone, and benzene can be used.
The reaction time varies depending on the type of unsaturated compound to be used, but is completed in 30 minutes to 5 hours.

  When the polyamine (d3) and the compound having an unsaturated double bond and a hydroxyl group (d4) are essential, the compound having an unsaturated double bond is based on 1 mol of the primary amino group of the polyamine (d3). The unsaturated double bond is preferably reacted at a rate of 0.1 to 1.0 mol, more preferably at a rate of 0.2 to 0.98 mol.

<Isocyanate group-containing polyurethane polyurea (D3)>
The isocyanate group-containing polyurethaneurea (D3) has an isocyanate group-excessive isocyanate group in the urethane prepolymer (D1) having a terminal isocyanato group and a secondary amino group in the polyamine compound (D2) having a hydroxyl group. It is made to react under conditions. The hydroxyl group in the polyamine compound (D2) having a hydroxyl group can also react with the isocyanate group in the urethane prepolymer (D1). However, since the amino group is more reactive than the hydroxyl group, the amino group is preferentially used. Reacts with isocyanate groups to form urea bonds. By this reaction, the isocyanate group-containing polyurethaneurea (D3) has a hydroxyl group derived from the polyamine compound (D2) having an isocyanate group at the end of the main chain and a hydroxyl group in the side chain.

<A compound having an amino group and a hydroxyl group (D4)>
The compound (D4) having an amino group and a hydroxyl group is obtained by reacting the amino group in the compound with the isocyanate group at the end of the main chain in the isocyanate group-containing polyurethane urea (D3) to obtain a polyurethane (D) having a hydroxyl group. These are used as so-called reaction terminators. Also in this case, since the amino group is more reactive with the isocyanate group than the hydroxyl group, it reacts preferentially with the isocyanate group at the end of the main chain in the isocyanate group-containing polyurethaneurea (D3). By reacting the amino group to an approximately equivalent amount as compared with the isocyanate group, the isocyanate group disappears, and as a result of the reaction, the polyurethane (D) having a hydroxyl group has a hydroxyl group derived from the polyamino compound (D2) having a hydroxyl group. It has a hydroxyl group derived from the compound (D4) having an amino group and a hydroxyl group in the chain at the end of the main chain. The polyurethane (D) having a hydroxyl group becomes a so-called main agent of the urethane-based pressure-sensitive adhesive.
In addition, since the compound (D4) having an amino group and a hydroxyl group is used as a so-called reaction terminator, it is important that one amino group is present in one molecule, and the hydroxyl group is also present in one molecule. One is preferred.

  Examples of (D4) include dialkylamines such as diethylamine, di-n-butylamine, di-n-octylamine, dicyclohexylamine, diisononylamine, monoethanolamine, diethanolamine, 2-amino-2-methyl- Monoamines having a hydroxyl group such as 1-propanol, tri (hydroxymethyl) aminomethane, 2-amino-2-ethyl-1,3-propanediol, 2-aminopropanol, 3-aminopropanol, monomethylhydrazine, 1,1- Alkyl hydrazines such as dimethyl hydrazine and benzyl hydrazine, hydrazides such as form hydrazide, aceto hydrazide, lauric acid hydrazide, N, N-dimethyl-1,3-propanediamine, N, N diethyl 1,3-propanediamine and the like One side is class 3 A monoamine compound having a mino group and a primary amino group can be used.

  Among the above reaction terminators (D4), monoamines having a hydroxyl group such as 2-amino-2-methyl-propanol can obtain a Michael addition type urethane urea resin having a hydroxyl group at the end, and are excellent in storage stability. Further, when a polyisocyanate-based curing agent is added to the Michael addition type urethane urea resin and crosslinked, it also serves as a crosslinking site. In the case of a monoamine having a hydroxyl group, both the amino group and the hydroxyl group can react with the terminal isocyanate group of the Michael addition type urethane urea resin, but the reactivity of the amino group is higher, and it reacts preferentially with the isocyanate group.

A method for obtaining a polyurethane (D) having a hydroxyl group as a main component of the urethane-based pressure-sensitive adhesive will be described more specifically.
As described above, the polyurethane (D) having a hydroxyl group is a polyurethane polyurea produced from the isocyanate group-containing urethane prepolymer (D1), the polyamino compound (D2) having a hydroxyl group, and the compound (D4) having an amino group and a hydroxyl group. And
1) A method in which a urethane prepolymer (D1) solution is charged into a reaction vessel, and a solution containing a polyamino compound (D2) or a compound having an amino group and a hydroxyl group (D4) is dropped,
2) A method in which a solution containing a polyamino compound (D2) or a compound (D4) having an amino group and a hydroxyl group is charged into a reaction vessel, and a urethane prepolymer (D1) solution is dropped,
It is divided roughly into. A method that results in a stable reaction is preferred. If there is no problem in the reaction, the method 1) that is easy to operate is preferred. In the method 1), as described above, the polyurethane prepolymer (D1), the polyamino compound (D2) and the isocyanate group are reacted so as to leave an isocyanate group to obtain a polyurethane polyurea (D3), and the isocyanate group in the polyurethane polyurea (D3) It is preferable to react the amino group in the compound (D4) having a group and a hydroxyl group.

The temperature of the urea reaction is preferably 100 ° C. or less. More preferably, it is 70 degrees C or less. Even at 70 ° C., the reaction rate is high, and when it cannot be controlled, 50 ° C. or less is more preferable. When the temperature is higher than 100 ° C., it becomes difficult to control the reaction rate.
When an alcohol solvent is used as a synthetic solvent for the amine compound (D2), the temperature in the reaction system is preferably 50 ° C. or lower, more preferably 40 ° C. or lower when the amine compound (D2) is dropped. It is preferable to keep.
The end point of the reaction can be confirmed by measuring isocyanate% due to titration, disappearance of isocyanate peak by IR measurement, or the like.

The weight average molecular weight of the polyurethane (D) having a hydroxyl group used in the present invention is preferably 10,000 or more in terms of a standard polystyrene equivalent molecular weight by GPC. More preferably, it is 30,000 or more. When the weight average molecular weight is less than 10,000, the adhesive properties, particularly the holding power, are remarkably lowered, which is not preferable.
The solution viscosity of the polyurethane (D) having a hydroxyl group used in the present invention is preferably 1000 to 10,000 cps (25 ° C.) at a solid content of 50%, more preferably 1000 to 5000 cps (at a solid content of 50%). 25 ° C.). If the viscosity is too high, the coating process for obtaining the pressure-sensitive adhesive laminate may be difficult, and if it is too low, a resin having a sufficient molecular weight may not be formed.

<Polyisocyanate Compound (E)> A urethane-based pressure-sensitive adhesive can be obtained by blending the polyurethane (D) as a main component and the polyisocyanate compound (E) as a curing agent. By reacting the hydroxyl groups of the main chain and side chain in the polyurethane (D) with the polyisocyanate compound (E), a urethane-based pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive laminate of the present invention is formed.
As the curing agent (E) used in the present invention, those exemplified as the aforementioned polyisocyanate compound (d2) can be used. Among them, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), xylylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) ( Non-yellowing type or hard yellowing type polyisocyanate compounds such as hydrogenated MDI) are preferred from the viewpoint of weather resistance, and hexamethylene diisocyanate (HDI) is more preferred because of easy control of the reaction. An adduct body is more preferable.

  The compounding ratio of the polyurethane (D) having a hydroxyl group and the polyisocyanate compound (E) used in the present invention is 0.5 to 10 parts by weight of the curing agent (E) with respect to the polyurethane (D). When the curing agent (E) is less than 0.5 parts by weight, the cohesive force is reduced, and when it is more than 10 parts by weight, the adhesive force is reduced. Preferably it is 1-5 weight part.

[Components for liquid crystal cells]
Among the pressure-sensitive adhesive laminates of the present invention using the above-mentioned acrylic pressure-sensitive adhesive and urethane pressure-sensitive adhesive, the optical film pressure-sensitive adhesive sheet is a peelable sheet, an acrylic pressure-sensitive adhesive layer, a urethane pressure-sensitive adhesive layer, and The optical films are sequentially laminated and can be obtained by various methods as described above.
Then, the peelable sheet is peeled off from the optical film pressure-sensitive adhesive sheet, and the exposed acrylic pressure-sensitive adhesive layer is adhered to the liquid-crystal cell glass member, whereby the liquid-crystal cell glass member, the acrylic pressure-sensitive adhesive layer, and the urethane-based pressure-sensitive adhesive layer. And the member for liquid crystal cells formed by laminating | stacking an optical film sequentially can be obtained.

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to this. In the following description, parts and% mean parts by weight and% by weight, respectively.

Synthesis example 1
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, 99.0 parts of n-butyl acrylate, 1.0 part of 4-hydroxybutyl acrylate, 150.0 parts of acetone, 2, 2 After charging 0.06 part of '-azobisisobutyronitrile and replacing the air in the reaction vessel with nitrogen gas, the temperature of the reaction solution was raised to 60 ° C. in a nitrogen atmosphere while stirring. Reacted for hours. After completion of the reaction, 190 parts of toluene, 0.25 part of acrylic acid and 0.50 part of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, the temperature was raised to 70 ° C., and the reaction was continued for 6 hours. I let you. After the reaction, 55 parts of toluene was added and cooled to room temperature to obtain a polymer having a solid content of 20.0%. Regarding the obtained polymer solution, the weight average molecular weight of the copolymer (A) is 1.6 million, the conversion rate during the synthesis of the copolymer (A) is 75.0%, and the weight average molecular weight of the copolymer (B) is The conversion rate during synthesis of 25000, copolymer (B) was 95%, and copolymer (B) was 32.0 parts relative to 100 parts of copolymer (A).

Synthesis example 2
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, 98.0 parts of n-butyl acrylate, 2.0 parts of 2-hydroxyethyl methacrylate, 150.0 parts of acetone, 2, 2 After charging 0.06 part of '-azobisisobutyronitrile and replacing the air in the reaction vessel with nitrogen gas, the temperature of the reaction solution was raised to 60 ° C. in a nitrogen atmosphere while stirring. Reacted for hours. After completion of the reaction, 190 parts of toluene, 0.52 part of methacrylic acid and 0.50 part of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, and the temperature was raised to 70 ° C. for 6 hours. Reacted. After the reaction, 55 parts of toluene was added and cooled to room temperature to obtain a polymer having a solid content of 20.0%. Regarding the obtained polymer solution, the weight average molecular weight of the copolymer (A) is 1,290,000, the conversion rate during the synthesis of the copolymer (A) is 74.0%, and the weight average molecular weight of the copolymer (B) is The conversion rate during synthesis of 24000, copolymer (B) was 91%, and the amount of copolymer (B) relative to 100 parts of copolymer (A) was 32.6 parts.

Synthesis example 3
In a 500 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirring blade, 95 parts of n-butyl acrylate, 5 parts of acrylic acid, 0.53 parts of 2,2′-azobisisobutyronitrile and 230 parts of ethyl acetate was charged, and the inside was replaced with nitrogen. Next, the temperature was raised to 60 ° C. and the reaction was allowed to proceed for 24 hours to obtain an acrylic ester polymer having a polymerization average molecular weight of 650,000.

Synthesis example 4
5 parts of adipic acid di2-ester (plasticizer) was added to 100 parts by weight of the polymer having the same composition as in Synthesis Example 3.

Synthesis Example 5 (Synthesis of polyamine (D2) having a hydroxyl group)
A 4-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel is charged with 400 g of isophoronediamine (IPDA) and 400 g of toluene, and 339 g of 4-hydroxybutyl acrylate and 301 g of butyl acrylate are added dropwise at room temperature. did. After completion of the dropwise addition, the mixture was reacted at 80 ° C. for 1 hour, and then 640 g of toluene was added to obtain a solution of compound (1) having one hydroxyl group and two secondary amino groups.

Synthesis Example 6
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 675 g of Kuraray polyol C-1090 (bifunctional polycarbonate diol, OH number 112, manufactured by Kuraray Co., Ltd.), isophorone diisocyanate (Hulus) (Japan Co., Ltd.) 225 g, toluene 225 g, dibutyltin dilaurate 0.075 g as a catalyst, gradually heated to 100 ° C., reacted for 2 hours, and confirmed the amount of isocyanate group remaining by titration, then cooled to 40 ° C. did.
Next, after adding 1857 g of ethyl acetate and 8.1 g of acetylacetone, 262 g of compound (1) dissolved in 180 g of ethyl acetate was added dropwise over 1 hour, and further aged for 1 hour to have an isocyanate group at the end of the main chain. After obtaining polyurethane polyurea (D3) having a hydroxyl group derived from compound (1) in the side chain, 5.5 g of 2-amino-2-methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.) was added, and NCO of IR chart It was confirmed that characteristic absorption (2270 cm @ -1) had disappeared, and a polyurethane polyurea having hydroxyl groups in the main chain and side chains was obtained.
The resulting polyurethanepolyurea solution was colorless and transparent and had a solid content of 30%, a viscosity of 13,400 cps, a number average molecular weight MN63,300, and a weight average molecular weight MW185,700.

Synthesis example 7
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 675 g of Kuraray polyol C-1090 (bifunctional polycarbonate diol, OH number 112, manufactured by Kuraray Co., Ltd.), isophorone diisocyanate (Hulus) (Japan Co., Ltd.) 225 g, toluene 225 g, dibutyltin dilaurate 0.075 g as a catalyst, gradually heated to 100 ° C., reacted for 2 hours, and confirmed the amount of isocyanate group remaining by titration, then cooled to 40 ° C. did.
Next, after adding 1859 g of ethyl acetate and 8.1 g of acetylacetone, 259 g of the compound (1) dissolved in 180 g of ethyl acetate was added dropwise over 1 hour and further aged for 1 hour to have an isocyanate group at the end of the main chain. After obtaining polyurethane polyurea (D3) having a hydroxyl group derived from compound (1) in the side chain, 0.9 g of 3-aminopropyltriethoxysilane (manufactured by Nippon Unicar Co., Ltd.) was added and aged for 10 minutes. Add 3.6 g of 2-amino-2-methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.) and confirm that the NCO characteristic absorption (2270 cm-1) of the IR chart has disappeared. Polyurethanepolyurea having a hydroxyl group was obtained.
The resulting polyurethanepolyurea solution was colorless and transparent and had a solid content of 30%, a viscosity of 4,400 cps, a number average molecular weight MN56,300, and a weight average molecular weight MW143,900.

In addition, the weight average molecular weight of a copolymer is the weight average molecular weight of polystyrene conversion calculated | required by GPC measurement, and GPC measurement conditions are as follows.
Apparatus: Shodex GPC System-21 (manufactured by Showa Denko KK)
Column: One Shodex KF-602.5, Shodex KF-606
A total of 3 Ms (2 manufactured by Showa Denko KK) are connected and used.
Solvent: Tetrahydrofuran Flow rate: 0.5 ml / min
Temperature: 40 ° C
Sample concentration: 0.1 wt%
Sample injection volume: 50 μl

Example 1
(Acrylic adhesive)
To 100 parts by weight of the polymer solution obtained in Synthesis Example 1, 0.05 part of XDI / TMP (trimethyllopepropane adduct of xylylene diisocyanate) was added and stirred well to prepare an acrylic adhesive. Got.
The acrylic pressure-sensitive adhesive was applied to a release-treated polyester film with an applicator so that the thickness when dried was 7 μm, and dried at 100 ° C. for 2 minutes to provide an acrylic pressure-sensitive adhesive layer.

(Urethane adhesive)
As a curing agent, 0.64 g of a 75% by weight ethyl acetate solution of hexamethylene diisocyanate trimethylolpropane adduct was added to 100 g of the urethane resin solution synthesized in Synthesis Example 6 to obtain a urethane-based adhesive. In terms of conversion, 0.48 g of hexamethylene diisocyanate corresponding to 1.5% by weight of the urethane resin synthesized in Synthesis Example 6 was blended with 32 g.
This urethane-based adhesive was applied to a release-treated polyester film with an applicator so that the thickness when dried was 20 μm, and dried at 100 ° C. for 2 minutes to provide a urethane adhesive layer.

Next, the obtained acrylic pressure-sensitive adhesive layer and urethane pressure-sensitive adhesive layer were bonded together to obtain a double-sided pressure-sensitive adhesive laminate in which both surfaces were covered with a peelable polyester film.
Next, the peelable polyester film on the urethane pressure-sensitive adhesive layer side was peeled off, and one side of the polarizing film was adhered to the urethane pressure-sensitive adhesive layer to obtain an optical film (polarizing film) pressure-sensitive adhesive sheet.

Prepare two sheets of 800 mm × 1500 mm polarizing film adhesive sheet, peel off the peelable polyester film on the acrylic adhesive layer side, respectively, and the polarizing film absorption axis on both sides of the 1.1 mm thick glass plate Acrylic pressure-sensitive adhesive layers were stuck so as to be orthogonal to each other, left in an autoclave at 50 ° C. and 5 atm for 30 minutes, taken out from the autoclave, and the presence or absence of bubbles entrained at the time of sticking was visually evaluated.
After evaluating the presence or absence of bubbles, the sample was held in an atmosphere of 60 ° C. and 90% RH for 500 hours to evaluate the presence / absence of floating / peeling and optical property maintenance.

<Air release evaluation>
○: There are no air bubbles involved during sticking.
(Triangle | delta): A part of bubble entrained at the time of sticking remains.
X: Almost air bubbles entrained at the time of sticking remain.

<Moisture and heat resistance test (floating / peeling)>
◎: When floating, peeling, and foaming are not recognized ○: When floating at the end and slight peeling is observed ×: When floating, peeling, and foaming are recognized

<Optical property maintenance test>
◎: When there is no decrease in the degree of polarization that affects visibility ○: When there is no decrease in the degree of polarization that affects visibility overall △: There is a decrease in the degree of polarization that affects visibility at the edges When slightly observed x: When a decrease in the degree of polarization affecting visibility is observed

Examples 2-8, Comparative Examples 1-2
A polarizing film pressure-sensitive adhesive sheet was obtained and evaluated in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive layer, the urethane pressure-sensitive adhesive layer, the film thickness of each layer, and the order of lamination were as shown in Table 1.

Claims (10)

An adhesive laminate comprising an acrylic adhesive layer and a urethane adhesive layer as essential constituent layers. The pressure-sensitive adhesive laminate according to claim 1, wherein a peelable sheet is further laminated on at least one surface of both the pressure-sensitive adhesive layer of the acrylic pressure-sensitive adhesive layer and the urethane pressure-sensitive adhesive layer. The pressure-sensitive adhesive laminate according to claim 2, wherein a peelable sheet, an acrylic pressure-sensitive adhesive layer, a urethane pressure-sensitive adhesive layer, and an optical film are sequentially laminated. 100 parts by weight of copolymer (A) having a weight average molecular weight of 1,000,000 to 2,000,000 and below, wherein the acrylic pressure-sensitive adhesive layer is obtained by radical copolymerization of the following monomers (a) and (b), 20 to 100 parts by weight of a copolymer (B) having a weight average molecular weight of 10,000 to 100,000, obtained by radical copolymerization of c) and (d), and the copolymer (A) and / or the copolymer The polyfunctional compound (C) having at least two reactive functional groups capable of reacting with (B) is formed from an acrylic pressure-sensitive adhesive containing 0.003 to 3 parts by weight. 3. The pressure-sensitive adhesive laminate according to any one of 3.
(a) a monomer having a reactive functional group and an ethylenically unsaturated double bond
(b) Other monomer having an ethylenically unsaturated double bond copolymerizable with (a) above
(c) Monomer having a carboxyl group and an ethylenically unsaturated double bond
(d) Other monomer having an ethylenically unsaturated double bond copolymerizable with the above (c) The acrylic pressure-sensitive adhesive contains a copolymer (B) obtained by radical copolymerization of the monomers (c) and (d) in the presence of the copolymer (A), and a polyfunctional compound (C). The pressure-sensitive adhesive laminate according to claim 4. The pressure-sensitive adhesive laminate according to any one of claims 1 to 5, wherein the urethane-based pressure-sensitive adhesive layer is formed of a urethane-based pressure-sensitive adhesive containing a polyurethane (D) having a hydroxyl group and a polyisocyanate compound (E). . The pressure-sensitive adhesive laminate according to claim 5, wherein the hydroxyl group content of the polyurethane (D) having a hydroxyl group is 1 × 10 ⁻⁵ to 1 × 10 ⁻³ (mol / g). Polyurethane (D) having a hydroxyl group is an isocyanate group-containing urethane prepolymer (D1) obtained by reacting a polyol (d1) and a polyisocyanate (d2) under conditions of excess isocyanate, and a polyamino compound (D2) having a hydroxyl group. It is a polyurethane polyurea having a hydroxyl group, which is obtained by reacting an isocyanate group-containing polyurethane polyurea (D3) obtained by reaction with an isocyanate-excess condition and a compound (D4) having an amino group and a hydroxyl group. The pressure-sensitive adhesive laminate according to claim 6 or 7. The pressure-sensitive adhesive according to claim 8, wherein the polyamino compound (D2) having a hydroxyl group is a compound obtained by Michael addition reaction of a polyamine (d3) and a compound (d4) having an unsaturated double bond and a hydroxyl group. Laminated body. A liquid crystal cell member in which a glass member for a liquid crystal cell, an acrylic pressure-sensitive adhesive layer, a urethane pressure-sensitive adhesive layer, and an optical film are sequentially laminated.