KR20060119762A - The method for producing acryl resin - Google Patents

Abstract

Provided is a method for preparing aryl resin obtained by radical polymerizing monomers in the presence of organic solvent, which has a high molecular weight, and a narrow molecular weight distribution, and a decreased amount of monomers. The method for preparing acryl resin comprises radical polymerizing (meth)acrylic acid ester(a) and a monomer comprising at least one polar functional groups selected from the group consisting of carboxyl, hydroxyl, amide, amino, epoxy, oxetanyl, aldehyde, and isocyanate groups, and one olefinically double bond in molecule(b), in the presence of organic solvent. In the method, during radical polymerization, organic solvent in the range of 5-100(parts by weight/hr) of R represented by the formula: R=[(AX(1-C)/C-100X(1-B)/B)/D]X100 is mixed to 100 parts by weight of the monomers used in the polymerization solution at initiation of polymerization.

Description

Production method of acrylic resin {THE METHOD FOR PRODUCING ACRYL RESIN}

(Patent Document 1) Japanese Patent Application Laid-Open No. 9-145925 [Claim 1], Example 1, Example 4, [Effects of the Invention]

This invention relates to the manufacturing method of the acrylic resin suitable for adhesion of an optical film and a glass base material.

Acrylic resins obtained by radical polymerization in the presence of an organic solvent are excellent in adhesive force, cohesion force, weather resistance, transparency, durability, and the like, and thus are widely used as pressure-sensitive adhesives for forming pressure-sensitive adhesive layers of pressure-sensitive adhesive tapes and pressure-sensitive adhesive sheets. In recent years, the adhesive is laminated | stacked on optical films, such as a polarizing film and retardation film, and glass base materials, such as a liquid crystal cell, are made to adhere to the adhesive layer obtained, and flats, such as a liquid crystal display device (LCD) and an organic electroluminescent (EL), etc. It is used for a panel display device (FPD).

The pressure-sensitive adhesive layer is required to suppress the peeling of the foam and the glass substrate under high temperature and high humidity conditions in conjunction with the high performance of the FPD, and as a preferable acrylic resin for such pressure-sensitive adhesive layer, (meth) acrylic acid ester as a main component Then, a monomer having a carboxyl group, a hydroxyl group or an amide group, an alkoxysilyl group-containing thiol compound which is a chain transfer agent, and an organic solvent are mixed together and then copolymerized to obtain a weight average molecular weight (Mw) of 800,000 to 1,500,000 and a molecular weight distribution (Mw / Mn) It is reported that the acrylic resin which is 1.5-3.5 is obtained (patent document 1). Moreover, even after peeling an optical film from a glass base material in order to fix it again, the adhesive containing this acrylic resin, a crosslinking agent, etc. hardly generate | occur | produce cloudiness, the residue of an adhesive, etc. on the surface of the glass base material which contacted the adhesive layer. It is also reported that the so-called reworkability is excellent.

MEANS TO SOLVE THE PROBLEM As a result of investigating the solution polymerization method which mixed the raw materials as described in patent document 1 collectively, about 20% of monomers, such as unreacted (meth) acrylic acid ester, remain, the monomer is not removed sufficiently. Otherwise, when the heat shock (hereinafter sometimes referred to as HS) is applied to 60 ° C. → -20 ° C. to 60 ° C. for 1 cycle and repeated 100 cycles, the monomers are repeatedly volatilized and aggregated, resulting in peeling or blurring of the glass plate surface. It became clear that there was a possibility of a back. An object of the present invention is an acrylic resin obtained by radical polymerization of a monomer in the presence of an organic solvent, wherein the weight average molecular weight of the resin is 1,000,000 or more, and the molecular weight distribution (Mw / Mn) of the resin is narrow to 5 or less. Moreover, it is providing the manufacturing method of the acrylic resin in which the monomer content contained in this resin was reduced.

The present invention is a method for producing an acrylic resin in which a (meth) acrylic acid ester (a) and the following monomer (b) are radically polymerized in the presence of an organic solvent, wherein the monomer 100 is used in the polymerization reaction solution at the start of polymerization. It is the manufacturing method of the acrylic resin characterized by mixing an organic solvent with R represented by Formula (1) within 5-100 (weight part / hr) within radical polymerization with respect to a weight part.

R = [(A × (1-C) / C-100 × (1-B) / B) / D] × 100 (1)

(In formula, A represents the total weight part of the monomer used for the polymerization reaction solution at the time of superposition | polymerization, and an acrylic resin, B represents the density | concentration (weight%) of the monomer contained in the polymerization reaction solution at the time of superposition | polymerization, and C is superposition | polymerization. The total concentration (% by weight) of the monomer and the acrylic resin contained in the polymerization reaction solution at the end is indicated, and D represents the polymerization time (hr).)

(b): A monomer containing at least one polar functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, an oxetanyl group, an aldehyde group and an isocyanate group and one olefinic double bond in the molecule.

Effects of the Invention

The acrylic resin obtained by the manufacturing method of this invention is a high molecular weight whose molecular weight distribution is 1,000,000 or more, molecular weight distribution (Mw / Mn) is 5 or less, and in the acrylic resin obtained, the reaction rate of a monomer is high, and monomer content is It reduces to 15 weight part or less with respect to 100 weight part of acrylic resin (solid content).

And although the adhesive which has the acrylic resin as a main component has little change in the appearance, such as foaming and whitening, in an adhesive layer, even if it is stored under high temperature and high humidity conditions, the peeling between an adhesive layer and a glass base material is suppressed, and HS resistance is also great.

Moreover, after attaching an optical film, such as a polarizing film, to a glass base material through the adhesive layer, even after peeling off the film from a glass base material in order to fix it again, the surface of the glass base material which contacted the adhesive layer was blurred, It is excellent in the so-called rework property that hardly any residue or the like is generated. Thereby, even if peeling the adhesive laminated | stacked once from a glass base material, it becomes suppressed that an adhesive agent remains or becomes cloudy on the surface of the glass base material after peeling, and can use it again as a glass base material.

To practice the invention  Best form for

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The acrylic resin produced in the present invention includes at least one polar functional group selected from the group consisting of (meth) acrylic acid ester (a) and a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, an oxetanyl group, an aldehyde group and an isocyanate group, It is an acrylic resin obtained by carrying out radical polymerization using the monomer (b) which contains one olefinic double bond in a molecule | numerator as an essential monomer.

(Meth) acrylic acid ester (a) in this invention is a compound represented by Formula (A).

(In formula (A), R <_1> represents a hydrogen atom or a methyl group, R <_2> represents a C1-C14 alkyl group or an aralkyl group. The alkyl group or aralkyl group of R <_2> is substituted by the C1-C10 alkoxy group. You may have it.)

Here, as (meth) acrylic acid ester (a), linear acrylic acid, such as methyl acrylate, ethyl acrylate, a propyl acrylate, n-butyl acrylate, n-octyl acrylate, lauryl acrylate, a stearyl acrylate, etc. Alkyl esters; branched alkyl acrylates such as iso-butyl acrylate, 2-ethylhexyl acrylate and iso-octyl acrylate; Linear methacrylate alkyl esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, lauryl methacrylate and stearyl methacrylate; and branched methacrylic acid alkyl esters such as iso-butyl methacrylate, 2-ethylhexyl methacrylate and iso-octyl methacrylate.

As (meth) acrylic acid ester in which the alkoxy group substituted by the hydrocarbon group of R <_2> , methoxy ethyl acrylate, ethoxy methyl acrylate, methoxy ethyl methacrylate, ethoxy methyl methacrylate etc. are mentioned, for example. .

Acrylic resin may contain the structural unit derived from different some (meth) acrylic acid ester. (Meth) acrylic acid ester (a) is 60-99.9 weight part normally, Preferably it is 80-99.6 weight part with respect to 100 weight part (non-volatile content) of acrylic resin.

As a monomer (b), for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid etc. are mentioned as monomer (b) whose polar functional group is a carboxyl group, As a monomer (b) whose polar functional group is a hydroxyl group, for example. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. are mentioned. Moreover, as a monomer (b) whose polar functional group is an amide group, acrylamide, methacrylamide, N, N- dimethylaminopropyl acrylamide, diacetonediamide, N, N- dimethyl acrylamide, N, N- Diethyl acrylamide, N-methylol acrylamide, etc. are mentioned, As a monomer (b) whose polar functional group is an epoxy group, glycidyl acrylate, glycidyl methacrylate, etc. are mentioned, for example, Polarity As a monomer (b) whose functional group is an oxetanyl group, it is oxetanyl (meth) acrylate, 3-oxetanylmethyl (meth) acrylate, (3-methyl-3- oxetanyl) methyl (meth), for example. ) Acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, etc. are mentioned. Moreover, as a monomer (b) whose polar functional group is an amino group, N, N- dimethylaminoethyl acrylate, allylamine, etc. are mentioned, for example, As a monomer (b) whose polar functional group is an isocyanate group, it is 2-, for example. Methacryloyl oxyethyl isocyanate etc. are mentioned, As a monomer (b) whose polar functional group is an aldehyde group, acrylaldehyde etc. are mentioned, for example. As these monomers (b), you may use combining two or more types of monomers (b).

Especially as a monomer (b), the monomer (e) whose polar functional group is a hydroxyl group, and the monomer (b) whose polar functional group is a carboxyl group are preferable, and 4-hydroxybutyl (meth) acrylate, acrylic acid, and 2-hydroxy are especially preferable. Ethyl (meth) acrylate is preferred.

As a usage-amount of the monomer (b) used of this invention, it is about 0.1-20 weight part with respect to 100 weight part of acrylic resin normally. If the amount of the monomer (b) is 0.1 parts by weight or more, the cohesive force of the resin obtained tends to be improved, and if it is 20 parts by weight or less, the pressure-sensitive adhesive layer follows the dimensional change even if the optical film changes, Since there exists a tendency for the lifting and peeling between a glass substrate and an adhesive layer to be suppressed, it is preferable.

In the manufacturing method of this invention, you may use monomers other than (meth) acrylic acid ester (a) and monomer (b).

Specifically, the monomer (c) which contains one olefinic double bond in a molecule | numerator, and a heterocyclic group of at least 1 5-membered ring or more in a molecule | numerator can be illustrated. The heterocyclic group of at least one 5-membered ring or more means a group in which at least one methylene group of an alicyclic hydrocarbon group having 5 or more carbon atoms, preferably 5 to 7 carbon atoms is substituted with a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom.

Specific examples of the monomer (c) include acryloyl morpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, and caprolactone modified tetrahydro. Furfuryl acrylate etc. are mentioned. In addition, monomers in which heteroatoms constitute 3-membered rings and 7-membered rings, such as 3,4-epoxycyclohexylmethyl acrylate and 3,4-epoxycyclohexylmethyl methacrylate, have a heterocyclic group having a 7-membered ring. Because of monomer (c). Moreover, olefinic double bond may be contained in the heterocyclic group like 2, 5- dihydrofuran etc. You may use two or more types of monomers (c) different as monomer (c).

Especially as a monomer (c), N-vinylpyrrolidone, vinyl caprolactam, acryloyl morpholine, or a mixture thereof is preferable.

As the usage-amount of the monomer (c) in the manufacturing method of this invention, it is about 30 weight part or less normally with respect to 100 weight part of acrylic resin, Preferably it is about 0.1-20 weight part. When the monomer (c) is used, even if the size of the optical film changes, the pressure-sensitive adhesive layer follows the size change and changes, so that there is no difference between the brightness of the periphery of the liquid crystal cell and the brightness of the center part, and whitening and color unevenness are suppressed. Since it exists in the tendency to become, it is preferable, and since it exists in the tendency for the lifting and peeling between a glass substrate and an adhesive layer to be 30 weight part or less, it is preferable.

As a monomer different from any of (meth) acrylic acid ester (a), a monomer (b), and a monomer (c), as a monomer (d) used for an acrylic resin, the monomer containing an at least 2 olefinic double bond in a molecule | numerator is used. It can be illustrated. By the presence of this monomer (d), the main chain composed of the structural unit (a) or the like of the acrylic resin is crosslinked. As a specific example of a monomer (d), as a monomer (bifunctional monomer) which contains two olefinic double bonds in a molecule | numerator, such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, etc. Bis (meth) acrylamides, such as (meth) acrylates, methylenebis (meth) acrylamide, and ethylenebis (meth) acrylamide, divinyl esters, such as divinyl adipic acid and divinyl sebacate, allyl meta Acrylate, divinylbenzene, and the like. Moreover, as a monomer (trifunctional vinyl monomer) which contains three olefinic double bonds in a molecule | numerator, 1,3,5-triacryloyl hexahydro-S-triazine, a triallyl isocyanurate, a triallyl Amine, N, N- diallyl acrylamide, etc. are mentioned, As a monomer (tetrafunctional vinyl monomer) which contains four olefinic double bonds in a molecule | numerator, tetramethylol methane tetraacrylate and tetraallyl pyromellitate , N, N, N ', N'-tetraallyl-1,4-diaminobutane, tetraallyl ammonium salt, etc. are mentioned. You may use two or more types of monomers (d) different as monomer (d).

Among the monomers (d), monomers having two (meth) acryloyl groups represented by the following formula (D) in a molecule are preferable.

(Wherein R ₃ represents a hydrogen atom or a methyl group)

As a usage-amount of the monomer (d) in the manufacturing method of this invention, it is about 5 weight part or less with respect to 100 weight part of acrylic resin, Preferably it is about 0.1-3 weight part. When the monomer (d) is used, even if the size of the optical film changes, the pressure-sensitive adhesive layer follows and changes in the size change, so that there is no difference between the brightness of the periphery of the liquid crystal cell and the brightness of the central part, and whitening and color unevenness are suppressed. It is preferable to have a tendency to become, and when it is 5 weight part or less, since generation | occurrence | production of a gel tends to be suppressed when manufacturing an acrylic resin, it is preferable.

As a monomer (e) used for an acrylic resin as another monomer other than any of (meth) acrylic acid ester (a), a monomer (b), a monomer (c), and a monomer (d), it is one olefinic double bond in a molecule | numerator. And the monomer containing at least one alicyclic structure is illustrated. The alicyclic structure is usually a cycloparaffin structure or cycloolefin structure having 5 or more carbon atoms, preferably about 5 to 7 carbon atoms. Here, a cycloolefin structure is a structure containing an olefinic double bond in an alicyclic structure.

Specifically, as an acrylic ester having an alicyclic structure, isobornyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, cyclododecyl acrylate, methylcyclohexyl acrylate, trimethylcyclohexyl acrylate, tert-butylcyclohexyl acrylate The cyclohexyl alpha ethoxy acrylate, cyclohexyl phenyl acrylate, etc. are mentioned, As methacrylic acid ester which has an alicyclic structure, for example, isobornyl methacrylate, cyclohexyl methacrylate, methacryl Acid dicyclopentanyl, cyclododecyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, cyclohexyl alpha ethoxy methacrylate, cyclohexylphenyl methacrylate, etc. Can be mentioned. Examples of the acrylate containing a plurality of alicyclic structures include biscyclohexyl methyl itaconate, dicyclooctyl itaconate, dicyclododecyl methyl succinate, and vinyl cyclohexyl acetate containing vinyl groups. Monomer (e).

As a monomer (e), you may use combining two or more types of monomers (e).

As the usage-amount of the monomer (e) used for the manufacturing method of this invention, it is about 30 weight part or less with respect to 100 weight part of acrylic resin normally, Preferably it is about 0.1-15 weight part. When the monomer (e) is used, there is a tendency that the lifting or peeling between the glass substrate and the pressure-sensitive adhesive layer is suppressed and is preferable, and if it is 30 parts by weight or less, even if the size of the optical film changes, the pressure-sensitive adhesive layer follows the size change and changes. Therefore, since there is no difference between the brightness of the periphery of the liquid crystal cell and the brightness of the central part, whitening and color unevenness tend to be suppressed, which is preferable.

Especially as a monomer (e), isobornyl acrylate, cyclohexyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, and dicyclopentanyl acrylate are preferable.

In the manufacturing method of this invention, you may use the vinylic monomer (f) different from any of monomers (a)-(e). Examples of the vinyl monomers include fatty acid vinyl esters, vinyl halides, vinylidene halides, aromatic vinyls, (meth) acrylonitrile, and conjugated diene compounds.

Here, as fatty acid vinyl ester, vinyl acetate, a vinyl propionate, a vinyl butyrate, a vinyl 2-ethylhexanoate, a vinyl laurate, etc. are mentioned, for example. Vinyl chloride, vinyl bromide, etc. are illustrated as vinyl halide, vinylidene chloride, etc. are illustrated as vinylidene halide, and acrylonitrile and methacrylonitrile are illustrated as (meth) acrylonitrile. The conjugated diene compound is an olefin having a conjugated double bond in a molecule, and specific examples thereof include isoprene, butadiene, and chloroprene. Aromatic vinyl is a compound having a vinyl group and an aromatic group, and specific examples include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, Styrene-based monomers such as octyl styrene, fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodine styrene, nitrostyrene, acetyl styrene and methoxy styrene, and nitrogen-containing aromatic vinyl such as vinylpyridine and vinyl carbazole Can be mentioned. You may use combining these 2 or more types of monomers (f) as these vinylic monomers (f).

It is preferable that the usage-amount of the monomer (f) used for the manufacturing method of this invention is 5 weight part or less normally with respect to 100 weight part of acrylic resins, Preferably it is 0.05 weight part or less, Especially preferably, it is not used substantially.

The manufacturing method of this invention is a manufacturing method of the acrylic resin which radical-polymerizes a (meth) acrylic acid ester (a) and a monomer (b) as an essential monomer in presence of an organic solvent, and mixes an organic solvent at a specific mixing rate during superposition | polymerization. It is a manufacturing method characterized by the above-mentioned.

Here, as an organic solvent, For example, aromatic hydrocarbons, such as toluene and xylene; Esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; aliphatic alcohols such as n-propyl alcohol and isopropyl alcohol; Ketones, such as methyl ethyl ketone and a methyl isobutyl ketone, etc. are mentioned.

One type of organic solvent is usually used from the viewpoint of easy recovery of the organic solvent, and a mixture of plural kinds may be used, or the organic solvent to be mixed during polymerization and the organic solvent may be different.

As a polymerization initiator used for radical polymerization, a thermal polymerization initiator, a photoinitiator, etc. are mentioned, for example, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) as a photoinitiator, for example. ) Ketones and the like. As a thermal polymerization initiator, it is 2,2'- azobisisobutyronitrile, 2,2'- azobis (2-methylbutyronitrile), 1,1'- azobis (cyclohexane-1-, for example). Carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2 Azo compounds such as' -azobis (2-methylpropionate) and 2,2'-azobis (2-hydroxymethylpropionitrile); Lauryl peroxide, tert-butylhydroperoxide, benzoyl peroxide, tert-butylperoxybenzoate, cumene hydroperoxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, tert-butylperoxyneo Organic peroxides such as decanoate, tert-butylperoxypivalate, and (3,5,5-trimethylhexanoyl) peroxide; Inorganic peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide and the like. Moreover, the redox type initiator etc. which used the thermal polymerization initiator and the reducing agent together can also be used as a polymerization initiator.

As a polymerization initiator, although it selects suitably according to reaction temperature and polymerization conditions especially, a thermal polymerization initiator is preferable at the point of industrially using solution polymerization, and especially an azo compound has a short half life and it is hard to produce a side reaction, and it is a viewpoint of productivity. Preferred at

As a usage-amount of the polymerization initiator used for this invention, it is about 0.001-0.3 weight part normally with respect to 100 weight part of all monomers, Preferably it is about 0.01-0.2 weight part. If it is 0.001 weight part or more, a polymer is preferable at the point which becomes high molecular weight, and since 0.3 weight part is high, there exists a tendency for a monomer reaction rate to improve, and it is preferable.

As a mixing method of a polymerization initiator, although it is a method of mixing collectively at the time of a polymerization start, for example, 80-99%, preferably 90-95% of the usage-amount of a polymerization initiator is mixed together at the time of a polymerization start, and a monomer When the concentration of is about 10% by weight or less, in order to further reduce the monomer concentration, a method of mixing the remaining polymerization initiator, for example, 1 to 20%, preferably 5 to 15% of the amount of the polymerization initiator is polymerized. The method of mixing collectively at the time of start, and mixing the remaining polymerization initiator with the organic solvent, etc. are mentioned.

With respect to 100 parts by weight of the monomer used in the polymerization reaction solution at the start of the polymerization, the mixing rate (parts by weight / hr) of the organic solvent during radical polymerization is R to 5 to 100 (parts by weight / hr) represented by the formula (1). This is the mixing speed within the range of.

R = [(A × (1-C) / C-100 × (1-B) / B) / D] × 100 (1)

(In formula, A represents the total weight part of the monomer used for the polymerization reaction solution at the time of superposition | polymerization, and an acrylic resin, B represents the density | concentration (weight%) of the monomer contained in the polymerization reaction solution at the time of superposition | polymerization, and C is superposition | polymerization. The total concentration (% by weight) of the monomer and the acrylic resin contained in the polymerization reaction solution at the end is indicated, and D represents the polymerization time (hr).)

Here, 100 weight part of monomers used for the polymerization reaction solution at the time of a polymerization start means that not only the usage-amount of the monomer at the time of polymerization start, but also the usage-amount of the monomer mixed when mixing a monomer with an organic solvent are included.

A represents the total weight part of the monomer and acrylic resin used for the polymerization reaction solution at the time of completion | finish of polymerization, and the total weight part of the monomer and acrylic resin contained in a polymerization reaction solution was used by the point that superposition | polymerization of an acrylic resin is an addition reaction. Since this coincides with the total weight of the monomer, the value may be used.

The use amount A of the monomer at the end of the polymerization is usually 120 parts by weight or less, preferably 110 parts by weight or less, and particularly preferably 100 parts by weight with respect to 100 parts by weight of the monomer used at the start of the polymerization. When the usage-amount of the monomer at the time of a polymerization start is 120 weight part or less, since the molecular weight of the acrylic resin obtained tends to improve, it is preferable.

B which is the density | concentration (weight%) of the monomer contained in the polymerization reaction solution at the time of superposition | polymerization start is 40 weight% or more normally, Preferably it is prepared at 50-60 weight%. If it is 40 weight% or more, since a high molecular weight polymer can be obtained, it is preferable. Moreover, since it exists in the tendency to suppress the rapid temperature rise by heat of polymerization, it is preferable that it is 60 weight% or less.

In addition, the density | concentration (weight%) of the monomer contained in a polymerization reaction solution can be measured by gas chromatography, liquid chromatography, etc., such as an absolute calibration method and an internal standard method.

In addition, the reaction rate of a monomer can be calculated | required by first obtaining the weight of an unreacted monomer from the weight of the polymerization reaction solution, and its concentration, and dividing the weight by the total weight of the used monomer.

C represents the total concentration (% by weight) of the monomer and the acrylic resin contained in the polymerization reaction solution at the end of the polymerization. Here, since the total concentration of the monomer and the acrylic resin contained in the polymerization reaction solution is an addition reaction, the polymerization weight of the acrylic resin can be obtained by dividing the total weight of the used monomers by the total weight of the polymerization reaction solution.

Therefore, [A × (1-C) / C-100 × (1-B) / B] × 100 is replaced with the amount of use (parts by weight) of the organic solvent mixed during the radical polymerization reaction later than the polymerization reaction start. Can be. As a weight of Ax (1-C) / C-100x (1-B) / B, ie, the organic solvent mixed during a polymerization reaction, 0.3-0.3 weight part with respect to 1 weight part of monomer total weight (A) normally used It is about 4 weight part, Preferably it is about 0.5-3.5 weight part.

C is 30 weight% or more normally, Preferably it is prepared at 30-40 weight%. If it is 30 weight% or more, since it exists in the tendency to suppress low molecular weight production | generation, even if monomer concentration becomes low in the latter part of reaction, it is preferable. Moreover, since it exists in the tendency for stirring the reaction solution at the time of superposition | polymerization to be 40 weight% or less, it is preferable.

Although polymerization time (hr) of D changes also with reaction temperature, it is 8 hours or more normally, and it is about 8 to 12 hours from an industrial viewpoint. When the polymerization time is 8 hours or more, the acrylic resin obtained is high in molecular weight, which is preferable because the reaction rate of the monomer at the end of polymerization tends to be improved.

R, that is, the mixing rate of the organic solvent mixed during the polymerization is 5 to 100 parts by weight / hr. When R is 5 weight part / hr or more, since stirring tends to become easy to stir the reaction solution at the time of superposition | polymerization, it is preferable, and when R is 100 weight part / hr or less, since the acrylic resin obtained tends to be high molecular weight. desirable.

Since mixing can calculate R if the value of A-D is determined, what is necessary is just to mix normally the organic solvent substantially continuously so that it may become this value.

Although mixing of the organic solvent may be intermittent, in this case, it is intermittently, preparing so that the density | concentration of acrylic resin (nonvolatile matter) except the monomer in a polymerization solution (hereinafter may be called reaction concentration) will be 50% or less. You may mix.

If the mixing of the organic solvent is continuous or intermittent, or the reaction concentration during the polymerization is 50% or less, it is preferable because the viscosity is sufficient to stir the polymerization reaction solution.

It is preferable not to use an alkoxy silyl group containing thiol compound substantially during superposition | polymerization. The alkoxysilyl group-containing thiol compound is not preferable because it tends to reduce the reaction rate of the monomer as a chain transfer agent. Here, substantially means the usage-amount below (Ax10 <^-5> weight part).

As a molecular weight of the acrylic resin obtained in this way, the weight average molecular weight (Mw) by standard polystyrene conversion of a gel permeation chromatography (GPC) is 1,000,000-2,000,000. When a weight average molecular weight is 1,000,000 or more, since the adhesiveness under high temperature, high humidity improves, there exists a tendency for the lifting and peeling between a glass substrate and an adhesion layer to fall, and also there exists a tendency for rework property to improve, and it is preferable. If the weight average molecular weight is 2,000,000 or less, even if the optical film changes in size, the adhesive layer follows and changes in the dimensional change, so that there is no difference between the brightness of the periphery of the liquid crystal cell and the brightness of the central part, and whitening and color unevenness are suppressed. It is preferable because it tends to be.

Moreover, as molecular weight distribution (weight average molecular weight / number average molecular weight (Mw / Mn)) of an acrylic resin, it is 5 or less, Preferably it is 3-4. If the molecular weight distribution is 5 or less, the cohesion force tends to be improved while maintaining the flexibility to a certain extent, and therefore it is preferable.

And the monomer concentration at the time of completion | finish of polymerization with respect to all the monomers used for superposition | polymerization is 85 weight% or more normally, Preferably it is 88 weight% or more. If it is 85 weight% or more, since the lifting and peeling between the adhesive layer obtained and a glass base material tend to be suppressed, it is preferable.

The acrylic resin obtained by the manufacturing method of this invention can be mix | blended with a crosslinking agent, and it can be set as an adhesive. Here, a crosslinking agent is what has a 2 or more functional group which can bridge | crosslink in the molecule | numerator which can bridge | crosslink the polar functional group derived from the monomer (b) contained in an acrylic resin, Specifically, an isocyanate type compound, an epoxy type compound, a metal chelate type compound, Aziridine type compounds etc. are illustrated.

Here, an isocyanate type compound is tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, Tetramethyl xylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, etc. are mentioned. Moreover, it is a crosslinking agent used by this invention also about what made the adduct and the isocyanate compound which made polyol, such as glycerol and a trimethylol propane, react with the said isocyanate compound as a 2, trimer, etc. in this invention.

As an epoxy type compound, the bisphenol-A epoxy resin, ethylene glycol glycidyl ether, polyethyleneglycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1, 6- hexanediol, for example Diglycidyl ether, trimethylolpropanetriglycidyl ether, diglycidyl aniline, N, N, N ', N'-tetraglycidyl-m-xylenediamine and 1,3-bis (N, N '-Diglycidylaminomethyl) cyclohexane and the like.

Examples of the metal chelate compound include compounds in which acetylacetone and ethyl acetoacetate are coordinated with polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium. Can be.

As an aziridine type compound, it is N, N'- diphenylmethane-4,4'-bis (1-aziridine carboxyl), N, N'-toluene-2,4-bis (1-aziri, for example). Dinecarboxamide), triethylenemelamine, bisisophthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N'-hexamethylene-1,6-bis ( 1-aziridinecarboxide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, and the like.

You may use two or more types of crosslinking agents as a crosslinking agent. As a usage-amount of the crosslinking agent (non-volatile content) in an adhesive, it is about 0.005-5 weight part with respect to 100 weight part (non-volatile content) of acrylic resin normally, Preferably it is about 0.01-3 weight part. When the amount of the crosslinking agent is 0.005 parts by weight or more, there is a tendency that the lifting peeling and reworkability between the glass substrate and the adhesive layer tends to be improved, and when the amount of the crosslinking agent is 5 parts by weight or less, the followability of the adhesive layer to the dimensional change of the optical film is preferred. Since it is excellent, there exists a tendency for whitening and color nonuniformity to fall, and it is preferable.

You may mix silane type compounds, such as a silane coupling agent and a silicone oligomer, in the adhesive in order to improve adhesiveness with a glass base material.

As a silane coupling agent, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl methyl dimethoxysilane, for example. , N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercapto Propyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropylethoxydimethylsilane, etc. Can be mentioned.

As a silicone oligomer, For example, 3-mercaptopropyl trimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyl trimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyl triethoxy Silane-tetramethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetra Ethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer, mercaptomethyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropyltrimethoxysilane-tetramethoxy Silane copolymer, 3-methacryloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropyl Ethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-metha Krilloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropyltriethoxysilane-tetraethoxysilane copolymer , 3-acryloxypropylmethyldimethoxysilane-tetramethoxysilane-depolymer, 3-acryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropylmethyldiethoxy Sisilane-tetramethoxysilane copolymer, 3-acryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer, vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane co Polymers, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxy Silane copolymer, vinylmethyldiethoxysilane-tetramethoxysilane copolymer, vinylmethyldiethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyl Trimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane co Polymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-amino propylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyl diethoxysilane- tetraethoxysilane copolymer, etc. are mentioned.

You may use two or more types of silane compounds for the adhesive of this invention.

As the usage-amount (solution) of the silane compound in an adhesive, it is about 0.0001-10 weight part with respect to 100 weight part (non-volatile content) of acrylic resin normally, Preferably it is used in the quantity of 0.01-5 weight part. It is preferable at the point which the adhesiveness of an adhesive layer and a glass substrate improves that the quantity of a silane type compound is 0.0001 weight part or more. Moreover, since the amount of a silane compound is 10 weight part or less, since there exists a tendency to suppress bleeding out of a silane compound from an adhesive layer, it is preferable.

The pressure-sensitive adhesive is composed of an acrylic resin, a crosslinking agent and / or a silane compound as described above, and may further contain a crosslinking catalyst, a weather stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, and the like. do.

Especially, if a crosslinking catalyst and a crosslinking agent are mix | blended with an adhesive, the optical film provided with the adhesive can be prepared by aging for a short time, and the optical laminated body containing this film can be lifted, peeling between an optical film and an adhesive layer, Foaming in an adhesive layer may be suppressed, and the rework property may be excellent.

As a crosslinking catalyst, for example, amines such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, triethylenediamine, polyamino resin and melamine resin A system compound etc. are mentioned. When using an amine compound as a crosslinking catalyst for an adhesive, an isocyanate type compound is preferable as a crosslinking agent.

The pressure-sensitive adhesive of the present invention is usually used as an optical film provided with a pressure-sensitive adhesive, for example, to be adhered with an optical film. As the manufacturing method, the adhesive diluted in the organic solvent is apply | coated, for example on a peeling film, it heats at 60-120 degreeC for about 0.5 to 10 minutes, and an organic solvent is distilled off and an adhesive layer is obtained. Subsequently, after attaching an optical film to an adhesive layer, after maturing about 5 to 20 days of atmospheric high surfaces with a temperature of 23 degreeC and a humidity of 65%, and fully reacting a crosslinking agent, the peeling film is peeled off and the optical film to which an adhesive was given is obtained. ; After obtaining an adhesive layer by the same method as the above, after combining the obtained peeling film and an adhesive layer in a multilayer by combining a peeling film and an adhesive layer, the temperature is 23 degreeC, and the humidity is 65% of humidity. In this case, after aging for about 5 to 20 days and the crosslinking agent is sufficiently reacted, a release film is peeled off, and instead, an optical film is attached to obtain an optical film to which an adhesive is applied.

Here, a peeling film is a base material at the time of forming an adhesive layer. It may be a base material which protects an adhesive layer from foreign substances, such as dust and a dust, during aging and when preserve | saving as an optical film provided with adhesive. As a specific example of a peeling film, the film which consists of various resins, such as a polyethylene terephthalate, a polybutylene terephthalate, a polycarbonate, and a polyallylate, is made into a base material, and it release-processes to a bonding surface with the adhesive layer of this base material (silicone) The process etc.) etc. were mentioned.

The optical film used for the optical film provided with the adhesive is a film which has optical characteristics, and a polarizing film, retardation film, etc. are mentioned, for example. A polarizing film is an optical film which has a function which emits polarized light with respect to incident light, such as natural light. As a polarizing film, the linear polarizing film which has the property which absorbs the linearly polarized light of the vibration surface parallel to an optical axis, and transmits the linearly polarized light which has a vertical vibration surface, and the polarization which reflects the linearly polarized light of the vibration surface parallel to an optical axis The elliptical polarizing film etc. which laminated | stacked the separation film, the polarizing film, and the retardation film mentioned later are mentioned. As a specific example of a polarizing film, the thing in which dichroic dyes, such as iodine and a dichroic dye, were adsorption-oriented to the polyvinyl alcohol film uniaxially stretched, etc. are mentioned.

Retardation film is an optical film having optical anisotropy such as uniaxial or biaxial, for example, polyvinyl alcohol, polycarbonate, polyester, polyallylate, polyimide, polyolefin, polystyrene, polysulfone, polyether sulfone, Stretching obtained by stretching a polymer film made of polyvinylidene fluoride / polymethyl methacrylate, liquid crystalline polyester, acetyl cellulose, cyclic polyolefin, ethylene-vinyl acetate copolymer saponified material, polyvinyl chloride and the like to about 1.01 to 6 times A film etc. are mentioned. Especially, the polymer film which uniaxially stretched and biaxially stretched polycarbonate or polyvinyl alcohol is preferable.

Examples of the retardation film include a uniaxial retardation film, a wide viewing angle retardation film, a low light modulus retardation film, a temperature compensated retardation film, an LC film (rod-shaped liquid crystal torsional orientation), a WV film (disc-type liquid crystal tilt alignment), and a NH film (rod type). Liquid crystal tilt orientation), VAC film (complete biaxially-oriented retardation film), newVAC film (biaxially-oriented retardation film), etc. are mentioned.

Further, a substrate film (Protective Film) further attached to one or both surfaces of these optical films is preferably used as the optical film. As a board | substrate film, for example, an acetyl cellulose type film, such as an acrylic resin film different from the acrylic resin of this invention, a cellulose acetate acetate film, a polyester resin film, an olefin resin film, a polycarbonate resin film, and a polyether ether ketone resin A film, a polysulfone resin film, etc. are mentioned. Ultraviolet absorbers, such as a salicylic acid ester compound, a benzophenone type compound, a benzotriazole type compound, a triazine type compound, a cyanoacrylate type compound, and a nickel complex salt type compound, may be mix | blended with the board | substrate film. Among the substrate films, acetyl cellulose-based films are preferable.

The optical laminated body of this invention is a laminated body by which an optical film and a glass base material are laminated | stacked through an adhesive. An optical laminated body can attach and manufacture the adhesive layer and glass substrate of the optical film with which the adhesive was provided normally. Here, as a glass substrate, the glass substrate of a liquid crystal cell, glass for glare-proof, glass for sunglass, etc. are mentioned, for example. Especially, the adhesive of the optical film (lower plate polarizing plate) which attached the adhesive layer of the optical film (upper polarizing plate) to which the adhesive was attached to the glass substrate of the upper part of a liquid crystal cell, and the other adhesive was attached to the glass substrate of the lower part of a liquid crystal cell. Since the optical laminated body which affixes a layer can be used as a liquid crystal display device, it is preferable. As a material of a glass substrate, soda-lime glass, low alkali glass, an alkali free glass, etc. are mentioned, for example.

Since the optical laminated body of this invention hardly generate | occur | produces cloudiness, the remainder of an adhesive, etc. on the surface of the glass substrate which contacted the adhesive layer even after peeling the optical film provided with the adhesive from the optical laminated body, to the peeled glass substrate Again, the reworking of the optical film provided with the pressure-sensitive adhesive can be easily performed, that is, the reworkability is excellent.

Example

Hereinafter, an Example is given and this invention is demonstrated further more concretely. In addition, "part" and "%" in an Example are a basis of weight unless there is particular notice. In addition, the non volatile matter was measured by the measuring method based on JISK-5407. Specifically, the solution containing the acrylic resin is taken in a shale by an arbitrary weight, and the residual non-volatile content weight after drying for 2 hours at 115 ° C. in an explosion-proof oven is expressed as a ratio with respect to the weight of the solution initially measured. A viscosity is the value measured with the Brookfield viscometer at 25 degreeC. The weight average molecular weight is in terms of standard polystyrene using an apparatus, sample concentration 5㎎ / ㎖, the sample introduced amount 100㎕, a column Toso (Note) TSKgel G6000H _XL 2 Preparation of dog, in which the sequential series of TSKgel G5000H _XL 2 Dog It used and calculated | required using tetrahydrofuran as an eluent on the conditions of the temperature of 40 degreeC, and flow rate 1 ml / min.

The ratio of residual monomer at the time of completion | finish of polymerization with respect to all the monomers used for superposition | polymerization (Hereinafter, it may be called reaction rate) was calculated | required as follows.

(1) All the monomers used for the polymerization were weighed accurately in a sample bottle separately, about 0.005 g, about 0.05 g, and about 0.5 g, respectively, and diluted to 25 ml with ethyl acetate to prepare a standard solution. 1 μl of the standard solution was added to the measuring device, and the conditions of the monomers were measured by measuring the retention time and the peak area of the monomers, weighing the peak area on the horizontal axis and the weight of each monomer on the vertical axis, Qi) was obtained respectively.

(2) About 2.5 g of the reaction solution at the end of the polymerization was accurately weighed, diluted to 25 ml with ethyl acetate, the sample was measured under the same conditions as in (1), and the peak area of the monomer contained in the sample. Was measured. From these measurement results, the reaction rate of the monomer was obtained by the following formula.

(3) Reaction rate (%) = 100-Σ {Qi × (peak area of monomer i)} / sample weight × 100

(Wherein Qi represents the factor of monomer i)

(Measuring conditions)

Gas Chromatograph: Agilent 6850 Series Gas Chromatograph Filler; Capillary column (Del Science Co., Ltd., Liquid phase: TC-FFAP, Length: 30m × 0.53mm, I.D: 1.0㎛)

Injection temperature; 180 ℃

Detector temperature; 220 ℃

Column temperature; After holding at 50 ° C. × 10 minutes, the temperature was raised to 170 ° C. at 5 ° C./min, 10 ° C./min from 170 ° C. to 220 ° C., measurement time; 50 minutes

(Example 1)

81.8 parts of acetone, 98.9 parts of butyl acrylate (hereinafter referred to as BA) as the monomer (a), and 1.1 parts of acrylic acid as the monomer (b) to the reactor equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer After adding the mixed solution, replacing the air in the apparatus with nitrogen gas to make oxygen free, raising the internal temperature to 55 ° C., and then dissolving 0.14 parts of azobisisobutyronitrile (hereinafter referred to as AIBN) in 10 parts of acetone. The whole amount was added. 1 hour after the initiator was added, the acetone solvent was continuously added to the reactor at an addition rate of 17.3 parts by weight so that the concentration of the acrylic resin (hereinafter sometimes referred to as reaction concentration) except the monomer was 35% by weight. It was kept at 56 ° C for 12 hours, and finally, ethyl acetate solvent was added to adjust the reaction concentration to 20%. The weight average molecular weight 1,200,000 and Mw / Mn obtained the acrylic resin of 3.9 and the reaction rate 92.5% of a monomer.

(Example 2)

Into the same reactor as in Example 1, 81.8 parts of acetone, 83.7 parts of BA as the monomer (a), 15.2 parts of isobornyl acrylate (hereinafter referred to as AIB), and 1.1 parts of AA as the monomer (b) were placed in a nitrogen gas. After raising the internal temperature to 55 degreeC, replacing the air in an apparatus and making it oxygen-free, the whole quantity of the solution which melt | dissolved 0.14 part of AIBN in 10 parts of acetone was added. Subsequently, it reacted, mixing the organic solvent similarly to Example 1, and obtained the acrylic resin of the weight average molecular weight 1,220,000 and Mw / Mn as 3.3 and the reaction rate of 90.5% of a monomer.

(Example 3)

Into the same reactor as in Example 1, a mixed solution of 81.8 parts of acetone, 80.6 parts of BA as monomer (a), 15.2 parts of AIB, 3.1 parts of vinyl caprolactam (hereinafter referred to as VCL) and 1.1 parts of AA as monomer (b) was added thereto. The internal temperature was heated up to 55 degreeC, replacing the air in an apparatus with nitrogen gas, and oxygen-free, and then the whole amount of the solution which melt | dissolved 0.15 part of AIBN in 10 parts of acetone was added. Subsequently, it was made to react, mixing the organic solvent similarly to Example 1, and the weight average molecular weight 1,210,000 and Mw / Mn were 3.6 and the acrylic resin of 92.1% of the reaction rates of a monomer was obtained.

(Example 4)

Into the same reactor as in Example 1, 53.8 parts of acetone, 96.8 parts of BA as monomer (a), 2.1 parts of methyl acrylate (hereinafter referred to as MA), and 1.1 parts of AA as monomer (b) were placed in a device with nitrogen gas. After replacing air and making it oxygen-free, the internal temperature was heated up to 55 degreeC, and the total amount of the solution which melt | dissolved 0.08 part of AIBN in 10 parts of acetone was added. 1 hour after the initiator was added, the mixture was continuously added to the reactor at an addition rate of 89.7 parts by weight / hr so that the reaction concentration was 30% by weight, and the mixture was kept at an internal temperature of 54 to 56 ° C for 12 hours. The reaction concentration was adjusted to 20%. The weight average molecular weight 1,350,000 and Mw / Mn obtained the acrylic resin of 4.1 and the reaction rate 92.7% of a monomer.

(Example 5)

Into the same reactor as in Example 1, 81.8 parts of acetone, 89.9 parts of BA as monomer (a), 5.7 parts of methyl methacrylate (hereinafter referred to as BMA), 3.4 parts of MA, and 1.0 parts of AA as monomer (b) were added, After raising the internal temperature to 55 degreeC, replacing the air in an apparatus with nitrogen gas and making it oxygen-free, the whole amount of the solution which melt | dissolved 0.13 parts of AIBN in 10 parts of acetone was added. 1 hour after the initiator was added, the mixture was continuously added to the reactor at 6.8 parts by weight / hr of the acetone solvent so that the reaction concentration was 40% by weight, followed by warming at an internal temperature of 54 to 56 ° C for 12 hours, and finally by adding an ethyl acetate solvent. The reaction concentration was adjusted to 20%. The weight average molecular weight 1,190,000 and Mw / Mn obtained the acrylic resin of 3.2 and the reaction rate of the monomer 89.2%.

(Example 6)

Into the same reactor as in Example 1, 66.7 parts of acetone, 98.9 parts of BA as the monomer (a), and 1.1 parts of AA as the monomer (b) were added, and the internal temperature was changed while replacing the air in the apparatus with nitrogen gas to make oxygen free. After heating up to 60 degreeC, the whole amount of the solution which melt | dissolved 0.14 part of AIBN in 10 parts of acetone was added. 1 hour after the initiator was added, the mixture was continuously added to the reactor at a rate of 39.7 parts by weight of acetone solvent at a reaction rate of 30% by weight, and kept at 59 to 61 ° C for 12 hours. Finally, an ethyl acetate solvent was added thereto. The reaction concentration was adjusted to 20%. The weight average molecular weight 1,270,000 and Mw / Mn obtained the acrylic resin of 3.8 and the reaction rate 93.5% of a monomer.

(Example 7)

Into the same reactor as in Example 1, 66.7 parts of acetone, 98.3 parts of BA as the monomer (a), and 1.7 parts of AA as the monomer (b) were added, and the internal temperature was changed while replacing the air in the apparatus with nitrogen gas to make oxygen free. After heating up to 55 degreeC, the whole amount of the solution which melt | dissolved 0.14 part of AIBN in 10 parts of acetone was added. After 2 hours of adding the initiator, 163.6 parts by weight of acetone solvent (81.8 parts by weight at an mixing rate of 81.8 parts by weight) was added to the reactor six times so that the reaction concentration was 35% by weight. It was kept for a while, and finally, ethyl acetate solvent was added to adjust the reaction concentration to 20%. The weight average molecular weight 1,320,000 and Mw / Mn of polystyrene conversion of GPC obtained 3.4 and the acrylic resin of 90.3% of reaction rates of a monomer.

(Comparative Example 1)

Into the same reactor as in Example 1, a mixed solution of 100 parts of acetone, 99.4 parts of BA as monomer (a), and 0.6 parts of AA as monomer (b) was added, and the inside of the apparatus was replaced with nitrogen gas so as to be oxygen free. After heating up at 60 degreeC, the whole amount of the solution which melt | dissolved 0.18 part of AIBN in 10 parts of acetone was added. 1 hour after the initiator was added, the mixture was continuously added to the reactor at an acetone solution feed rate of 133.3 parts by weight / hr so that the reaction concentration was 30% by weight, and the mixture was kept at 59 to 61 ° C for 6 hours, and finally, ethyl acetate solvent was added for reaction. The concentration was adjusted to 20%. The weight average molecular weight 800,000 and Mw / Mn obtained the acrylic resin of 6.5 and the reaction rate of 80.2% of monomers.

(Comparative Example 2)

Into the same reactor as in Example 1, 81.8 parts of acetone, 98.9 parts of BA as the monomer (a), and 1.1 parts of AA as the monomer (b) were added thereto, and the internal temperature was changed while replacing the air in the apparatus with nitrogen gas to make oxygen free. After heating up to 45 degreeC, the whole amount of the solution which melt | dissolved 0.01 part of azobis (2, 4- dimethylvaleronitrile) in 10 parts of acetone was added. After 1 hour of adding the initiator, the mixture was kept at 44 to 46 ° C for 10 hours while being continuously supplied to the reactor at an addition rate of 17.1 parts by weight of acetone so that the reaction concentration was 45% by weight, and finally, an ethyl acetate solvent was added. The reaction concentration was adjusted to 20%. The weight average molecular weight 2,500,000 and Mw / Mn of polystyrene conversion of GPC were 3.4 and the reaction rate of the monomer was 80.4%. The monomer composition and the results of the polymerization examples are shown in Table 1.

Example 1 Example 2 Example 3 Example 4 Example 5 Monomer (parts by weight) BA 98.9 83.7 80.6 96.8 89.9 AA 1.1 1.1 1.1 1.1 1.0 AIB 15.2 15.2 VCL 3.1 MA 2.1 3.4 BMA 5.7 Sum (A = A ') 100 100 100 100 100 density B (%) 55 55 55 65 55 C (%) 35 35 35 30 40 solvent Initial weight part 81.8 81.8 81.8 53.8 81.8 Addition time (hr) 6 6 6 2 10 [(A × (1-C) / C-100 × (1-B) / B) × 100 (parts by weight) Amount of organic solvent used 103.9 103.9 103.9 179.5 68.2 Mixing Speed R (parts per hour) 17.3 17.3 17.3 89.7 6.8 Amount of Organic Solvents Mixed (Initial Magnification) 1.3 1.3 1.3 3.3 0.8 Intermittent addition count continuity continuity continuity continuity continuity Weight average molecular weight (Mw × 10 ⁶ ) 1.20 1.22 1.21 1.35 1.19 Molecular Weight Distribution (Mw / Mn) 3.9 3.3 3.6 4.1 3.2 Monomer Reaction Rate (%) 92.5 90.5 92.1 92.7 89.2

Example 6 Example 7 Comparative Example 1 Comparative Example 2 Monomer (parts by weight) BA 98.9 98.3 99.4 98.9 AA 1.1 1.7 0.6 1.1 AIB VCL MA BMA Sum (A = A ') 100 100 100 100 density B (%) 60 55 50 55 C (%) 35 35 30 45 solvent Initial weight part 66.7 81.8 100.0 81.8 Addition time (hr) 3 6 One 12 [(A × (1-C) / C-100 × (1-B) / B) × 100 (parts by weight) Amount of organic solvent used 119.0 103.9 133.3 40.4 Mixing Speed R (parts per hour) 39.7 17.3 133.3 3.4 Amount of Organic Solvents Mixed (Initial Magnification) 1.8 1.3 1.3 0.5 Intermittent addition count continuity 6 continuity continuity Weight average molecular weight (Mw × 10 ⁶ ) 1.27 1.32 0.80 2.50 Molecular Weight Distribution (Mw / Mn) 3.8 3.5 6.5 3.4 Monomer Reaction Rate (%) 93.5 90.3 80.2 80.4

BA: Butyl acrylate (monomer (a))

BMA: Butyl methacrylate (monomer (a))

MA: Methyl acrylate (monomer (a))

AA: acrylic acid (monomer (b))

AIB: isobornyl acrylate (monomer (e))

VCL: vinyl caprolactam (monomer (c))

<Production Example of Adhesive>

A polyisocyanate compound (trade name: Takenate D-160N, manufactured by Mitsuda Keda Chemical), which is a crosslinking agent, and a silane compound (trade name: KBM803, Shin-Etsu Kasei) , Adhesives 1-7 (using the acrylic resin of Examples 1-7) and adhesives 8 and 9 (using the acrylic resin of Comparative Examples 1 and 2) were obtained. Table 2 shows the mixing amounts of the crosslinking agent (non-volatile content) and the silane compound (non-volatile content) with respect to 100 parts of the acrylic resin (non-volatile content).

<Production Example of Optical Laminate>

The adhesive obtained in this way was apply | coated so that the thickness after drying might be set to 25 micrometers on the mold release process surface of the polyethylene terephthalate film (Lintec company make, brand name: PET3811) release-processed using an applicator, and it dried at 90 degreeC for 1 minute, A sheet-like adhesive was obtained. Subsequently, a polarizing film (film having a three-layer structure sandwiched by a triacetylcellulose protective film on both surfaces of an adsorbed and stretched iodine in polyvinyl alcohol) was used as the optical film. After attaching the surface which has the adhesive obtained in the above by the laminator, it aged for 10 days on conditions of the temperature of 23 degreeC, and humidity of 65%, and obtained the optical film with adhesive which the adhesive layer was formed. Subsequently, the optical film provided with the adhesive was attached so that it may cross nicol on the glass substrate for liquid crystal cells (made by Corning Corporation, 1737), and the optical laminated body was obtained. When this is stored at 80 ° C. in a dry atmosphere for 96 hours (heat resistance), and when stored at 60 ° C. and 90% RH for 96 hours (heat and humidity resistance), after heating to 60 ° C., the temperature is reduced to −20 ° C. and then to 60 ° C. When the temperature raising process was carried out for one cycle (one hour) and stored for 100 cycles, the durability of the optical laminate after storage and the expression state of whitening were observed visually at each condition (1). The results were classified into the following tips and shown in Table 2.

<Whitening of Optical Laminates>

The expression state of whitening was evaluated in the following four steps.

(Double-circle): Whitening is not observed at all.

(Circle): Whitening is hardly noticeable.

(Triangle | delta): The whitening is conspicuous slightly.

X: Whitening is remarkably confirmed.

<Heat resistance, moist heat resistance, HS resistance of the optical laminate>

The durability was evaluated in the following four steps.

(Double-circle): No external appearance changes, such as lifting, peeling, and foaming, are observed.

○: Almost no change in appearance such as lifting, peeling or foaming is observed.

(Triangle | delta): The appearance change, such as lifting, peeling, foaming, is slightly outstanding.

X: Appearance changes, such as lifting, peeling, foaming, are remarkably confirmed.

<Reworkability>

Reworkability was evaluated as follows. First, the optical laminated body was prepared with the test piece of 25 mm x 150 mm. Next, this test piece was affixed on the glass substrate for liquid crystal cells using the sticking apparatus (The Fuji Plastic Machinery Co., Ltd. product "Ramipaka"), and autoclave-processed at 50 degreeC and 5 kg / cm <2> (490.3 kPa) for 20 minutes. . Subsequently, after heat-processing at 70 degreeC for 2 hours, and storing for 48 hours in 50 degreeC oven, this adhesion test piece is peeled to 180 degree direction at a speed of 300 mm / min in 23 degreeC and 50% RH atmosphere of relative humidity, Table 2 shows the results of observing the state of the glass plate surface classified in the following manner.

The reworkability was evaluated by the following four stages by the state of the glass plate surface.

(Double-circle): A blur and the residue of an adhesive agent are not observed at all on the glass plate surface.

(Circle): Blur etc. are hardly confirmed on the glass plate surface.

(Triangle | delta): A cloudy etc. are confirmed by the glass plate surface.

X: The adhesive residue is confirmed on the glass plate surface.

Adhesive layer Takenate D-160N KBM803 all sorts of flowers Heat resistance Heat resistant HS Rework Example 1 Adhesive 1 0.06part 0.4 part ○ ○ ◎ ○ ○ Example 2 Adhesive 2 0.06part 0.4 part ○ ○ ○ ◎ ○ Example 3 Adhesive 3 0.14part 0.4 part ◎ ○ ○ ◎ ○ Example 4 Adhesive 4 0.05 parts 0.4 part ○ ○ ◎ ○ ◎ Example 5 Adhesive 5 0.06part 0.4 part ○ ○ ◎ ○ ○ Example 6 Adhesive 6 0.06part 0.4 part ○ ○ ◎ ○ ◎ Example 7 Adhesive 7 0.06part 0.4 part ○ ○ ○ ◎ ○ Comparative Example 1 Adhesive 8 0.3 part 0.4 part ○ × △ × △ Comparative Example 2 Adhesive 9 0.06part 0.4 part △ △ × × ○

Including the optical laminate of the present invention, for example, notebook type, desktop type, liquid crystal display for PC, such as PDA (Personal Digital Assistance), liquid crystal television, on-vehicle display, electronic dictionary, digital camera, digital video camera, electronic Liquid crystal display devices, such as a calculator and a clock, are mentioned.

Claims (5)

In the manufacturing method of the acrylic resin which radically polymerizes (meth) acrylic acid ester (a) and the following monomer (b) as an essential monomer in presence of an organic solvent, with respect to 100 weight part of monomers used for the polymerization reaction solution at the time of a polymerization start, The organic solvent is mixed in the range whose R represented by Formula (1) is 5-100 (weight part / hr) during radical polymerization, The manufacturing method of the acrylic resin characterized by the above-mentioned. R = [(A × (1-C) / C-100 × (1-B) / B) / D] × 100 (1) (In formula, A represents the total weight part of the monomer used for the polymerization reaction solution at the time of superposition | polymerization, and an acrylic resin, B represents the density | concentration (weight%) of the monomer contained in the polymerization reaction solution at the time of superposition | polymerization, and C is superposition | polymerization. The total concentration (% by weight) of the monomer and the acrylic resin contained in the polymerization reaction solution at the end is indicated, and D represents the polymerization time (hr).) (b): A monomer containing at least one polar functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, an oxetanyl group, an aldehyde group and an isocyanate group and one olefinic double bond in the molecule. The method of claim 1, The manufacturing method characterized by adjusting the mixing speed of the organic solvent so that the density | concentration of acrylic resin (non-volatile content) except the monomer in the polymerization solution of acrylic resin may be 50 weight% or less. The method according to claim 1 or 2, The organic solvent is at least one organic solvent selected from the group consisting of aromatic hydrocarbons, esters, aliphatic alcohols and ketones. The adhesive containing the acrylic resin obtained by the manufacturing method of Claims 1-3, a crosslinking agent, and a silane compound. The laminated body in which an optical film and a glass base material are laminated | stacked through the adhesive of Claim 4.