JP2007126559A5 - - Google Patents

Description

Acrylic resin composition and pressure-sensitive adhesive

  The present invention relates to an acrylic resin composition and an adhesive containing the acrylic resin composition.

A liquid crystal cell generally used in a liquid crystal display device such as a TFT or STN has a structure in which a liquid crystal component is sandwiched between two glass substrates . On the surface of the glass substrate, through an adhesive composed mainly of an acrylic resin, a polarizing film, optical films such as retardation films are laminated. And the optical laminated body formed by laminating a glass substrate, a pressure-sensitive adhesive and an optical film in order is first to produce an optical film with a pressure-sensitive adhesive obtained by laminating the pressure-sensitive adhesive on the optical film, and then the surface of the pressure-sensitive adhesive A method of laminating a glass substrate is generally used.
Such an optical film with pressure-sensitive adhesive is susceptible to curling because of a large dimensional change due to expansion and contraction under heat or wet heat conditions, and foams within the pressure-sensitive adhesive layer of the obtained optical laminate, or the pressure-sensitive adhesive layer and the glass substrate. floating between the wood, peeling off or the like is disadvantageously or generated. In addition, the distribution of residual stress acting on the optical film with adhesive becomes non-uniform under heat or wet heat conditions, resulting in stress concentration at the outer periphery of the optical laminate, resulting in white spots in the TN liquid crystal cell (TFT), STN liquid crystal There was a problem that color unevenness occurred in the cell.
In order to solve this problem, Patent Document 1 proposes an acrylic resin composition comprising a high molecular weight acrylic resin having a weight average molecular weight of 600,000 to 2,000,000 and a low molecular weight acrylic resin having a weight average molecular weight of 500,000 or less.

JP 2000-109771 A [Claim 1]

Although recently it has been attempted to use a liquid crystal display device as in-vehicle such as a car navigation system, by suppressing the foaming of an adhesive layer at a high temperature in a vehicle, it bubbles, floating, peeling off, etc. Heat resistance that does not change appearance, white spot resistance that white spots do not occur under high temperature conditions, durability that appearance changes such as foaming, floating, and peeling do not occur under high humidity conditions, and heating -Heat shock resistance has also become necessary, such that appearance changes such as foaming, floating and peeling do not occur even when cooling is repeated.
The present inventors examined an optical laminate obtained by laminating an optical film on an adhesive composed of a composition of a high molecular weight acrylic resin and a low molecular weight acrylic resin satisfying the conditions described in Patent Document 1 . However, it has become clear that heat resistance, white spot resistance, durability, and heat shock resistance may not be satisfied.
The objective of this invention is providing the acrylic resin composition suitable for the adhesive which gives the optical laminated body which is excellent in heat resistance, white spot resistance, durability, and heat shock resistance.

（式中、Ｒ ₁ は水素原子又はメチル基を表し、
Ｒ ₂ は炭素数１〜１４のアルキル基又はアラルキル基を表すが、Ｒ ₂ のアルキル基の水素原子又はアラルキル基の水素原子は炭素数１〜１０のアルコキシ基によって置換されていてもよい。）
で表される（メタ）アクリル酸エステルに由来する構造単位（ａ）を主成分とし、少なくとも一つの水酸基と一つのオレフィン性二重結合を分子内に含有する単量体に由来する構造単位（ｂ）を０.１〜１０mol％含有し、カルボキシル基、アミド基、アミノ基、エポキシ基、オキセタニル基、アルデヒド基及びイソシアネート基からなる群から選ばれる少なくとも一つの極性官能基と、一つのオレフィン性二重結合を分子内に含有する単量体に由来する構造単位（ｃ）を任意成分として０.０１mol％以下含有してもよい、重量平均分子量が 50,000〜500,000であるアクリル樹脂（１）と、
上記構造単位（ａ）を主成分とし、上記構造単位（ｃ）を０.５〜８mol％含有し、上記構造単位（ｂ）を含有してもよい、重量平均分子量が 1,000,000〜1,500,000 であるアクリル樹脂（２）とからなり、
アクリル樹脂（１）及び（２）の合計１００重量部に対し、アクリル樹脂（１）を１０〜５０重量部含有するアクリル樹脂組成物であって、
アクリル樹脂（１）に含まれる構造単位（ｂ）に由来する水酸基濃度［ｂ］と、アクリル樹脂（２）に含まれる構造単位（ｂ）に由来する水酸基濃度［ｂ'］と、アクリル樹脂（２）に含まれる構造単位（ｃ）に由来する極性官能基濃度［ｃ］との関係が式（Ｉ）を充足することを特徴とするアクリル樹脂組成物である。 Under such circumstances, the present inventors have carried out intensive investigations and found that the viscosity Chakuzai, specific adhesive, found that it is possible to solve the above problems and completed the present invention.
That is, the present invention provides the following formula (A):

(Wherein R ₁ represents a hydrogen atom or a methyl group,
R ₂ represents an alkyl group having 1 to 14 carbon atoms or an aralkyl group, and the hydrogen atom of the alkyl group of R ₂ or the hydrogen atom of the aralkyl group may be substituted with an alkoxy group having 1 to 10 carbon atoms. )
A structural unit derived from a monomer having a structural unit (a) derived from a (meth) acrylic acid ester represented by the following formula as a main component and containing at least one hydroxyl group and one olefinic double bond in the molecule ( b) 0.1 to 10 mol%, at least one polar functional group selected from the group consisting of carboxyl group, amide group, amino group, epoxy group, oxetanyl group, aldehyde group and isocyanate group, and one olefinic property double bond structural unit derived from a monomer containing in the molecule (c) as an optional component may contain less 0 .01mol%, an acrylic resin having a weight average molecular weight of 50,000-500,000 (1) When,
The structural units (a) as a main component, the structural unit (c) containing 0.5～8Mol%, may contain the structural units (b), the weight average molecular weight of 1,000,000～1,500,000 acrylic Resin (2)
100 parts by weight of the total of the acrylic resin (1) and (2), an acrylic resin composition containing 10 to 50 parts by weight of acrylic resin (1),
A hydroxyl group concentration [b] derived from the structural unit (b) contained in the acrylic resin (1), a hydroxyl group concentration [b ′] derived from the structural unit (b) contained in the acrylic resin (2), and an acrylic resin ( The acrylic resin composition is characterized in that the relationship with the polar functional group concentration [c] derived from the structural unit (c) contained in 2) satisfies the formula (I).

6 ≦ [b / (b + b ′ + c)] × 100 ≦ 50 (I)
Here, the densities [b], [b ′] and [c] are values corresponding to the following equations, respectively.

The present invention also provides a pressure-sensitive adhesive obtained by blending the above acrylic resin composition and a crosslinking agent, a pressure-sensitive adhesive optical film obtained by laminating the pressure-sensitive adhesive on both sides or one side of an optical film, and the pressure-sensitive adhesive optical An optical laminate in which a glass substrate is laminated on the pressure-sensitive adhesive layer of the film is also provided.

The acrylic resin composition of the present invention, by applying a high hydroxyl group concentration in the low molecular weight of the acrylic resin (1), excellent flexibility, may given excellent adhesion for such an optical film. Moreover, when the optical film with an adhesive which laminated | stacked the optical film and this adhesive is laminated | stacked, for example on the glass substrate of a liquid crystal cell, the optical laminated body of this invention will be given. In such an optical laminate, the pressure-sensitive adhesive layer absorbs and relaxes stress caused by dimensional changes of the optical film and the glass substrate under wet heat conditions, so that local stress concentration is reduced and the pressure-sensitive adhesive layer floats on the glass substrate. , Peeling is suppressed. In addition, since optical defects due to non-uniform stress distribution are prevented, white spots are suppressed when the glass substrate is a TN liquid crystal cell (TFT).
Furthermore, even after the film is peeled from the optical laminate for re-attaching the optical film with the pressure-sensitive adhesive, the surface of the glass substrate that has been in contact with the pressure-sensitive adhesive layer hardly generates fogging, adhesive residue, or the like. Excellent reworkability. By this, even if the optical film with adhesive once laminated is peeled off from the glass substrate of the optical laminate, adhesive residue and fogging are suppressed on the surface of the glass substrate after peeling, and it can be used again as a glass substrate. .

Hereinafter, the present invention will be described in detail.
The monomer giving the acrylic resin used in the present invention (1) and structural unit comprising a Oite main component (2) (a), represented by the formula (A) (meth) acrylic acid ester. In the formula (A) , R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents an alkyl group having 1 to 14 carbon atoms or an aralkyl group. The hydrogen atom of the aralkyl group of R ₂ or the hydrogen atom of the alkyl group may be substituted with an alkoxy group having 1 to 10 carbon atoms.

The (meth) acrylic acid ester represented by the formula (A), for example, methyl acrylate, ethyl acrylate, propyl acrylate, n- butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n- octyl acrylate, isooctyl acrylate , lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, isobornyl acrylate, benzyl acrylate, acrylic acid esters such as methoxyethyl acrylate and ethoxymethyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n- butyl methacrylate, isobutyl methacrylate, 2 - ethylhexyl methacrylate, n- octyl methacrylate, isooctyl meth click relay , Lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, benzyl methacrylate, can be mentioned methacrylic acid esters such as methoxyethyl methacrylate and ethoxyethyl methacrylate.
These (meth) acrylic acid esters may be used two different types than the above.

And have you to A acrylic resin (1), the content of the formula (A) (meth) structural units derived from acrylic acid ester (a) is usually about 70～99.9Mol%, preferably Is 90-99.4 mol%. When the structural unit (a) is 99.9 mol% or less, the content of the structural unit (b) derived from the monomer containing a hydroxyl group described later tends to increase, and the binding site with the crosslinking agent tends to increase. This is preferable.
Also, you have your acrylic resin (2), the content of the structural unit derived from (meth) acrylic acid ester (a) is a normally 70-99. About 5 mol%, preferably 90 to 99. 4 mol% . When the structural unit (a) is at 99. 5 mol% or less, increases the content of the structural unit (c) derived from a monomer containing the later-described polar functional groups, the binding site of the cross-linking agent increases This is preferable because of the tendency to

The structural unit (b) derived from a monomer containing at least one hydroxyl group and one olefinic double bond in the molecule (hereinafter sometimes referred to as “hydroxyl group-containing monomer” ) is an acrylic resin (1 ) And an optional component in the acrylic resin (2) . Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. Two or more different hydroxyl group-containing monomers may be used in combination.

The structural unit (b) in the acrylic resin (1) is an essential component, and its content is 0.1 to 10 mol % . When the content of the structural unit (b ) in the acrylic resin (1) is 10 mol% or less, the cohesive force is improved, and the tendency of floating , peeling and foaming between the glass substrate and the pressure-sensitive adhesive layer is suppressed. This is preferable. Moreover, when it is 0.1 mol% or more, flexibility is improved and color unevenness tends to be suppressed, which is preferable.
The structural unit (b) in the acrylic resin (2) is an optional component, and its content is usually 10 mol% or less. When the content of the structural unit (b) is 10 mol% or less, the cohesive force is improved, and there is a tendency that floating and foaming between the glass substrate and the pressure-sensitive adhesive layer tend to be suppressed.

Monomer containing at least one polar functional group selected from the group consisting of carboxyl group, amide group, amino group, epoxy group, oxetanyl group, aldehyde group and isocyanate group and one olefinic double bond in the molecule The structural unit (c) derived from the body (hereinafter sometimes referred to as “polar functional group-containing monomer” ) is an essential component of the acrylic resin (2), and 0.01 mol% in the acrylic resin (1). Although it may contain below, it is preferable that an acrylic resin (1) does not contain this structural unit (c) substantially .

Specific examples of the polar functional group-containing monomer, as a monomer a polar functional group is a carboxyl group, for example, acrylic acid, methacrylic acid, maleic acid, and itaconic acid. Further, as the monomer a polar functional group is an amide group, such as acrylamide, methacrylamide, N, N-dimethylaminopropyl acrylamide, diacetone diamide, N, N-dimethylacrylamide, N, N-diethyl acrylamide, N -Methylolacrylamide etc. are mentioned.
It is a polar functional group is a monomer with an epoxy group, such as glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate. Here, a monomer in which an oxygen atom constitutes a 3-membered ring and a 7-membered ring, such as 3,4-epoxycyclohexylmethyl acrylate and 3,4-epoxycyclohexylmethyl methacrylate, is a highly reactive epoxy group. Therefore, it is a preferable monomer .
And polar functional group is a monomer which is a oxetanyl group, for example, oxetanyl (meth) acrylate, 3-oxetanylmethyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, (3- And ethyl-3-oxetanyl) methyl (meth) acrylate. Further, as a monomer a polar functional group is an amino group, for example, N, N-dimethylaminoethyl acrylate, allylamine and the like, is a monomer polar functional group is an isocyanate group , for example, 2-methacryloyloxyethyl isocyanate and the like, is a monomer polar functional group is an aldehyde group, for example, acrylic aldehydes.

These polar functional group-containing monomer, different two or more kinds may be used in combination above, but for example, containing at least one polar functional group selected from the group consisting of amino group and an epoxy-based single and dimers, such as a combination of a monomer having an isocyanate group, using polar functional group-containing monomers that can be reacted simultaneously from causing gelation during the polymerization of the acrylic resin, It is not preferable.
As the polar functional group-containing monomer , a monomer whose polar functional group is a carboxyl group is preferable, and acrylic acid is particularly preferable.

In the present invention , the content of the structural unit (c) in the acrylic resin (2) is 0.5 to 8 mol % . When the content of the structural unit (c) is at 0.5 mol% or more, preferably from the cohesive force of the resulting resin tends to be improved, is not more than 8 mol%, even if the dimension of an optical film changes Since the adhesive changes following the dimensional change, there is no difference between the brightness of the peripheral edge of the liquid crystal cell and the brightness of the central part, and there is a tendency to suppress white spots and uneven color phenomenon. preferable.

As a weight ratio (nonvolatile content) of the acrylic resins (1) and (2) in the acrylic resin composition of the present invention, the acrylic resin (1) is based on a total of 100 parts by weight of the acrylic resins (1) and (2). 10 to 50 parts by weight, preferably about 20 to 40 parts by weight. When the acrylic resin (1) is 10 parts by weight or more, even if the dimension of the optical film changes, the pressure-sensitive adhesive layer changes following the dimension change. This is preferable because there is no difference in brightness and white spots and color unevenness tend to be suppressed. When the acrylic resin (1) is 50 parts by weight or less, adhesion at high temperature and high humidity is improved. The float and peeling between the glass substrate and the pressure-sensitive adhesive layer tend to decrease, and the reworkability tends to improve, which is preferable.

The acrylic resin composition of the present invention is an acrylic resin composition containing 10 to 50 parts by weight of the acrylic resin (1) with respect to a total of 100 parts by weight of the acrylic resin (1) and the acrylic resin (2). The hydroxyl group concentration [b] derived from the structural unit (b) contained in 1), the hydroxyl group concentration [b ′] derived from the structural unit (b) contained in the acrylic resin (2), and contained in the composition relationship between the polar functional group concentration [c] derived from the structural unit (c) is one which satisfies the formula (I).
6 ≦ [b / (b + b ′ + c)] × 100 ≦ 50 (I)
Especially, it is preferable that [b / (b + b '+ c)] * 100 is 6-30.

Here, the hydroxyl group concentration [b] is obtained by dividing (mmol number of hydroxyl groups derived from the structural unit (b) contained in the acrylic resin (1)) by (g number of acrylic resin component in the acrylic resin composition). It represents value, hydroxyl group concentration [b '] is the (acrylic resin (mmol number of hydroxyl groups derived from the structural units (b) contained in 2)) (g number of the acrylic resin component of the acrylic resin composition) in represents the value obtained by dividing, polar functional group concentration [c] is an acrylic resin (acrylic resin (structural units contained in 2) (mmol number of polar functional groups derived from c)) (acrylic resin composition The value divided by the number of grams of the component).
In addition , the acrylic resin component in an acrylic resin composition represents solid content of the acrylic resin containing structural unit (a), such as acrylic resin (1) and (2).

[B / (b + b ′ + c) × 100] is 6 or more, that is, the hydroxyl group concentration [b] in the acrylic resin (1) is the hydroxyl group concentration ([b + b ′]) in the resin composition and the acrylic resin (2). When the concentration is 6% or more with respect to the total ([b + b ′ + c]) with the polar functional group concentration ([c]), the reaction between the acrylic resin (1) and the cross-linking agent increases, and white spots and uneven color phenomenon occur. Is preferable because of a tendency to be suppressed. Further, if the value is 50 or less, it is reduced crosslinking points of the acrylic resin (1) improved cohesion preferable because foaming is likely to be suppressed.

When the acrylic resin component in an acrylic resin composition consists only of acrylic resin (1) and (2), density | concentration [b] can be calculated | required by the following formula | equation (II) .
[B] = (X1 × Z1 × Y1 / 100) / M1 × 1000 / (X1 + X2) (II)
here,
X1: amount of the acrylic resin (1) (g) (nonvolatile content),
X2: The amount of the acrylic resin (2) (g) (nonvolatile content),
Y1: acrylic resin (1) charge of the hydroxyl group-containing monomers during manufacture (wt%),
M1: Molecular weight of the hydroxyl group-containing monomer used in the production of the acrylic resin (1) ,
Z1: Number of hydroxyl groups per molecule of the hydroxyl group-containing monomer used during the production of the acrylic resin (1) .
Incidentally, if the hydroxyl group-containing monomer and have contact to the acrylic resin (1) is used n species, the hydroxyl group concentration of the i-th monomer and [b] _i, be represented by [b] the following equation it can.

When the acrylic resin component in the acrylic resin composition is composed only of the acrylic resins (1) and (2), the concentration [b ′] can be obtained by the following formula (III) .
[B ′] = (X2 × Z2 × Y2 / 100) / M2 × 1000 / (X1 + X2) (III)
here,
Y2: Acrylic resin (2) the charged amount of the hydroxyl group-containing monomers during manufacture (wt%),
M2: molecular weight of the hydroxyl group-containing monomer used in the production of the acrylic resin (2) ,
Z2: The number of hydroxyl groups per molecule of the hydroxyl group-containing monomer used during the production of the acrylic resin (2) .
Incidentally, if the hydroxyl group-containing monomer and have your acrylic resin (2) is used n species, 'When _i, [b a hydroxyl group concentration of the i th monomer [b]'] is expressed by the following formula be able to.

When the acrylic resin component in the acrylic resin composition is composed only of the acrylic resins (1) and (2), the concentration [c] can be obtained by the following formula (IV) .
[C] = [X2 × Z3 × Y3 / 100] / M3 × 1000 / (X1 + X2) (IV)
here,
Y3: the acrylic resin (2) charge of polar functional group-containing monomer at the time of production (by weight%),
M3: The molecular weight of the polar functional group-containing monomer used in the production of acrylic resin (2),
Z3: The number of polar functional groups per molecule of the polar functional group-containing monomer used in the production of the acrylic resin (2) .
In the case where the polar functional group-containing monomer and have your acrylic resin (2) is used n species, the polar functional group concentration of the i-th monomer and [c] _i, [c] the following equation Can be expressed as

When the acrylic resins (1) and (2) used in the present invention are produced, they are further different from the (meth) acrylic acid ester, the hydroxyl group-containing monomer and the polar functional group-containing monomer. a body, one and the olefinic double bond in the molecule, a monomer containing a 5-membered ring or more cyclic structures may be copolymerized. Here, as a monomer containing a cyclic structure , for example, a monomer containing one olefinic double bond and an alicyclic structure in the molecule (hereinafter referred to as “ alicyclic monomer ” ) And a monomer containing one olefinic double bond and a heterocyclic structure in the molecule (hereinafter sometimes referred to as “ heterocyclic monomer ” ).

The alicyclic structure in the alicyclic monomer is usually a cycloparaffin structure or a cycloolefin structure having 5 or more carbon atoms, preferably about 5 to 7 carbon atoms. The cycloolefin structure contains an olefinic double bond in the alicyclic structure.
Specific monomers that contain one olefinic double bond and alicyclic structure in the molecule include isobornyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, cyclododecyl acrylate, and methylcyclohexyl. Acrylates having an alicyclic structure such as acrylate, trimethylcyclohexyl acrylate, tert-butylcyclohexyl acrylate, cyclohexyl α ethoxy acrylate, cyclohexyl phenyl acrylate; isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, methacrylic acid cyclododecyl, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, methacrylic acid tert- butyl cyclohexyl, cyclo hexyl phenyl meta click Examples thereof include methacrylic acid esters having an alicyclic structure such as relate.
Among these alicyclic monomers, isobornyl acrylate, cyclohexyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl acrylic acid, preferable because availability is easy.
Examples of the acrylate containing a plurality of alicyclic structures include biscyclohexylmethyl itaconate, dicyclooctyl itaconate, dicyclododecylmethyl succinate, and the like. Vinyl cyclohexyl acetate containing a vinyl group is also alicyclic simple. It is a mer .

The heterocyclic structure in the heterocyclic monomer means that at least one methylene group in the alicyclic hydrocarbon group having 5 or more carbon atoms, preferably 5 to 7 carbon atoms is a nitrogen atom, an oxygen atom or a sulfur atom. A heterocyclic group substituted with a heteroatom.
Specific examples include acryloylmorpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, caprolactone-modified tetrahydrofurfuryl acrylate, and the like. Furthermore, an olefinic double bond may be contained in the heterocyclic group such as 2,5-dihydrofuran. Among them, N-vinylpyrrolidone, vinylcaprolactam, and acryloylmorpholine are preferable as the monomer containing one olefinic double bond in the molecule and a heterocyclic structure.

As the monomer containing a cyclic structure, or may use different monomer.
Oite the A acrylic resin (1) or (2), the content of the structural unit derived from a monomer containing a cyclic structure (a "structural unit (d)"), relative to 100 parts by weight of an acrylic resin Usually, it is about 10 parts by weight or less. When the structural unit (d) is contained, even if the dimension of the optical film changes, the pressure-sensitive adhesive layer fluctuates following the change in dimension, so that the brightness between the peripheral edge of the liquid crystal cell and the brightness of the central part is between In some cases, the difference disappears and white spots and color unevenness are suppressed.

Further, in manufacturing the acrylic resin used in the present invention (1) and (2) may be co-polymerizing a vinyl monomer. Here, the vinyl monomer mentioned was the (meth) acrylic acid esters, hydroxyl group-containing monomer, the monomer having a polar functional group-containing monomer and a cyclic structure of a different monomeric those that have at least one vinyl group in the molecule, for example, vinyl esters, vinyl halides, vinylidene halides, conjugated diene compounds, styrene monomer, a nitrogen-containing aromatic vinyl, and (meth) acrylonitrile Can be mentioned.

Examples of the vinyl ester include monovinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate and vinyl laurate; and divinyl esters such as divinyl adipate and divinyl sebacate.
The halogenated vinyl, vinyl chloride, vinyl bromide and the like. Examples of the vinylidene halides, vinylidene chloride. Examples of the (meth) acrylonitrile, acrylonitrile, methacrylonitrile and the like.
The conjugated diene compound is an olefin having a conjugated double bond in the molecule, and specific examples include isoprene, butadiene and chloroprene.
Styrene monomers include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, fluorostyrene, chlorostyrene, bromo Examples thereof include styrene, dibromostyrene, iodostyrene, nitrostyrene, acetylstyrene, methoxystyrene , divinylbenzene and the like. Examples of the nitrogen-containing aromatic vinyl include vinyl pyridine and vinyl carbazole.

As vinyl monomers may be used more different monomers.
Oite acrylic resin (1) or (2), structural units of which from vinyl monomers, typically, to 100 parts by weight of an acrylic resin, 5 parts by weight or less, preferably below 0.05 part by weight Although it is , it is more preferable not to contain substantially.

Furthermore, when manufacturing acrylic resin (1) and (2) used for this invention, it has an above described (meth) acrylic acid ester, a hydroxyl-containing monomer, a polar functional group containing monomer, and a cyclic structure. A monomer that is different from the monomer and the vinyl monomer and that contains a plurality of olefinic double bonds in the molecule may be copolymerized . Examples of the monomer containing a plurality of olefinic double bonds in the molecule include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,3,5-triacryloylhexahydro-s-triazine. , (Meth) acrylates such as tetramethylolmethane tetraacrylate; bis (meth) acrylamides such as methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, N, N-diallylacrylamide; allyl (meth) acrylate, triallyl Examples include isocyanurate, triallylamine, tetraallyl pyromellitate, N, N, N ′, N′-tetraallyl-1,4-diaminobutane, and tetraallylammonium salt.

As the monomer containing a plurality of olefinic double bonds in the molecule, it may be used more different monomers.
Structure unit of derived from the acrylic resin (1) or (2) Oite, a monomer containing a plurality of olefinic double bonds in a molecule, usually, to 100 parts by weight of an acrylic resin, 5 parts by weight In the following, it is preferably 0.05 parts by weight or less , but more preferably substantially not contained.

Examples of the method for producing the acrylic resin (1) used in the present invention include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a suspension polymerization method.
In the preparation of the acrylic resin (1), a polymerization initiator is usually used. A polymerization initiator is used about 0.1-5 weight part with respect to a total of 100 weight part of all the monomers used for manufacture of an acrylic resin (1).

  Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone. Can be mentioned. Examples of the thermal polymerization initiator 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-methylpro) Azo compounds such as pionate) and 2,2'-azobis (2-hydroxymethylpropionitrile); lauryl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroper Oxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, tert-butylperoxide Organic peroxides such as xineodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide; inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide Can be mentioned. A redox initiator using a thermal polymerization initiator and a reducing agent in combination can also be used as the polymerization initiator.

As the method for producing the acrylic resin (1), the solution polymerization method is particularly preferable. As a specific example of the solution polymerization method, a desired monomer and an organic solvent are mixed to prepare a mixed solution having a monomer concentration of 20% by weight or more, preferably 30 to 60% by weight, and then in a nitrogen atmosphere. And a method of adding a polymerization initiator and stirring at about 40 to 90 ° C., preferably about 60 to 80 ° C. for about 3 to 10 hours. Further, in order to control the reaction, a monomer and a polymerization initiator or added during the polymerization, or may be it may be added after dissolved in an organic solvent used.
Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as n-propyl alcohol and isopropyl alcohol; methyl ethyl ketone and methyl isobutyl ketone. And ketones.

The molecular weight of the acrylic resin (1) thus obtained is a weight average molecular weight in terms of standard polystyrene by gel permeation chromatography (GPC) and is in the range of 50,000 to 500,000. When the weight average molecular weight is 50,000 or more, the adhesiveness under high temperature and high humidity is improved, and there is a tendency that floating and peeling between the glass substrate and the pressure-sensitive adhesive layer are reduced, and the reworkability is improved. If the weight average molecular weight is 500,000 or less, even if the dimension of the optical film changes, the pressure-sensitive adhesive layer changes following the dimensional change. This is preferable because there is no difference between the brightness and the brightness of the part, and white spots and color unevenness tend to be suppressed.

As a method for producing the acrylic resin used in the present invention (2), for example, a solution polymerization method, emulsion polymerization method, bulk polymerization method, include suspension polymerization method, solvent solution polymerization method among preferred. As a specific example of the solution polymerization method, a desired monomer and an organic solvent are mixed to prepare a mixed solution having a monomer concentration of 40% by weight or more, preferably 50 to 60% by weight, and then in a nitrogen atmosphere. at the polymerization initiator was added about 0.001 to 0.2 parts by weight, about 40 to 90 ° C., preferably 8 hours or more at about 50-70 ° C., and a method preferably for about 10-12 hours Is mentioned.
The thing similar to what was illustrated in the acrylic resin (1) can be used for the polymerization initiator in manufacture of an acrylic resin (2). The organic solvent can also be the same as those exemplified in the acrylic resin (1).

The molecular weight of the acrylic resin (2) thus obtained is in the range of 1,000,000 to 1,500,000 in terms of weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC). When the weight average molecular weight is 1,000,000 or more, the adhesiveness under high temperature and high humidity is improved, the floating and peeling between the glass substrate and the pressure-sensitive adhesive layer tend to be reduced, and the reworkability is improved. Therefore, it is preferable. If the weight average molecular weight is 1,500,000 or less, even if the dimensions of the optical film change, the pressure-sensitive adhesive layer fluctuates following the dimensional change. This is preferable because there is no difference between the two and there is a tendency to suppress white spots and color unevenness.

The pressure-sensitive adhesive of the present invention is obtained by blending a crosslinking agent with the acrylic resin composition thus obtained. The crosslinking agent used here has two or more functional groups capable of crosslinking with the hydroxyl group and / or polar functional group contained in the acrylic resin (2), specifically, an isocyanate compound, an epoxy. Examples of such compounds include metal compounds, metal chelate compounds, and aziridine compounds.
Here, as the isocyanate compound include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate , Triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate and the like. Moreover, glycerol in the isocyanate compound, adducts and obtained by reacting an a polyol Le of trimethylolpropane, even those in which the isocyanate compound is 2,3-mer, etc., can be used as a crosslinking agent in the present invention.

Examples of the epoxy compound include bisphenol A type epoxy resin, ethylene glycol glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylol propane tri Examples thereof include glycidyl ether, diglycidyl aniline, N, N, N ′, N′-tetraglycidyl-m-xylenediamine , and 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane.

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

Examples of the aziridine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxide), N, N′-toluene-2,4-bis (1-aziridinecarboxamide), triethylene Melamine, 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.

As the crosslinking agent, it may be used on a two or more types. As the crosslinking agent, an isocyanate compound is preferable because it can crosslink with the structural unit (b), which is an essential component of the acrylic resin (1), and in particular, tolylene diisocyanate, tolylene diisocyanate with glycerol and trimethylolpropane. adducts obtained by reacting an a polyol le such as those dimerization of tolylene diisocyanate, and at least one crosslinking agent selected from the group consisting of those trimerizing a tolylene isocyanate, structural units ( superior in reactivity with hydroxyl groups in b), lifting of the pressure-sensitive adhesive layer to the glass substrate, preferred because it tends to peel is inhibited.

The usage- amount of the crosslinking agent (nonvolatile content) in an adhesive is about 0.8-5 weight part normally with respect to 100 weight part (nonvolatile content) of acrylic resin, Preferably it is about 1-3 weight part. Specifically in Patent Document 1, a total of 100 parts by weight of the acrylic resin (1) and (2) to the (non-volatile matter), using 0.1 part by weight and 0.15 parts by weight of a crosslinking agent However, it is preferable that the amount of the crosslinking agent is 0.8 parts by weight or more, since the exfoliation and reworkability between the glass substrate and the pressure-sensitive adhesive layer tend to be improved, and is preferably 5 parts by weight or less. Since the followability of the pressure-sensitive adhesive layer is excellent with respect to the dimensional change of the optical film, white spots and color unevenness tend to decrease, which is preferable.

The pressure-sensitive adhesive of the present invention preferably contains a silane compound in order to improve the adhesion between the pressure-sensitive adhesive layer and the glass substrate. Silane-compounds may be either monomeric or oligomeric. Examples of the monomer of the silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxy Run, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl dimethoxymethyl silane, etc. 3-glycidoxypropyl ethoxy dimethylsilanylbis emissions and the like. Examples of the silane compound oligomer include 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane- Tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer, mercaptomethyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropyltrimethoxysilane- Tetramethoxysilane copolymer, vinyltrimethoxysilane-tetramethoxysilane copolymer, - aminopropyltrimethoxysilane - etc. tetramethoxysilane copolymers chromatography and the like.
The adhesive of the present invention may use two or more kinds of silane-based compounds.

The amount of the silane compound used in the pressure-sensitive adhesive is usually about 0.0001 to 10 parts by weight, preferably 0.01 to 5 parts by weight with respect to 100 parts by weight (nonvolatile content) of the acrylic resin composition. Used in. It is preferable that the amount of the silane compound is 0.0001 parts by weight or more because adhesion between the pressure-sensitive adhesive layer and the glass substrate is improved. Moreover, since it exists in the tendency which suppresses that a silane type compound bleeds out from an adhesive layer as the quantity of a silane type compound is 10 weight part or less, it is preferable.

The pressure-sensitive adhesive of the present invention contains the acrylic resin (1), the acrylic resin (2) and a crosslinking agent as described above, and preferably contains a silane compound, and further contains a crosslinking catalyst, a weathering stabilizer, and a tackifier. , plasticizers, softeners, dyes, pigments, may be added an inorganic filler, and the like.
Among them, when a crosslinking catalyst and a crosslinking agent are blended in the pressure-sensitive adhesive, an optical film with a pressure-sensitive adhesive can be prepared by aging in a short time, and the optical laminate including the film is between the optical film and the pressure-sensitive adhesive layer. floating, peeling or foaming of an adhesive layer is suppressed, moreover in some cases superior reworkability. Examples of the crosslinking catalyst include amine compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, triethylenediamine, polyamino resin , and melamine resin. When an amine compound is used as a crosslinking catalyst for the pressure-sensitive adhesive, an isocyanate compound is suitable as the crosslinking agent.

Adhesive attached optical film arm of the present invention are those consisting of the adhesive and the optical film, as its production method, for example, an adhesive is applied which is diluted in an organic solvent on a release film, 60 The pressure-sensitive adhesive layer is obtained by heating at ~ 120 ° C for about 0.5 to 10 minutes to distill off the organic solvent. Next, after pasting the optical film on the pressure-sensitive adhesive layer, in an atmosphere of 23 ° C. and 65% humidity, the film is aged for about 5 to 20 days, and after the crosslinking agent has reacted sufficiently, the release film is peeled off. Method for obtaining an optical film with an adhesive; after obtaining an adhesive layer in the same manner as described above, the release film and the adhesive layer are alternately laminated on the obtained laminate of the release film and the adhesive layer. After being combined in multiple layers, if the atmosphere is at 23 ° C. and humidity 65%, it is aged for 5 to 20 days, and after the crosslinking agent has reacted sufficiently, the release film is peeled off, and an optical film is pasted instead. And a method of further peeling the release film to obtain an optical film with an adhesive.
Here, a peeling film is a base material at the time of forming an adhesive layer. In some cases, it is a base material that protects the pressure-sensitive adhesive layer from foreign matters such as dust and dust during aging and storage as an optical film with pressure-sensitive adhesive. As a specific example of the release film, a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyarylate is used as a base material, and a release treatment (silicone treatment) is performed on the bonding surface with the adhesive layer of the base material. Etc.).

  The optical film used for the optical film with pressure-sensitive adhesive of the present invention is a film having optical properties, and examples thereof include a polarizing film and a retardation film. A polarizing film is an optical film having a function of emitting polarized light with respect to incident light such as natural light. As a polarizing film, a linearly polarizing film having a property of absorbing linearly polarized light having a vibrating surface parallel to the optical axis and transmitting linearly polarized light having a vibrating surface that is a vertical surface, parallel to the optical axis. Examples thereof include a polarizing separation film that reflects linearly polarized light on the vibration surface, and an elliptically polarizing film in which a polarizing film and a retardation film described later are laminated. Specific examples of the polarizing film include a film in which a dichroic dye such as iodine or a dichroic dye is adsorbed and oriented on a uniaxially stretched polyvinyl alcohol film.

The retardation film is an optical film having optical anisotropy such as uniaxial or biaxial, for example, polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, polystyrene, polysulfone, polyethersulfone, polysulfone By stretching a polymer film composed of vinylidene fluoride / polymethyl methacrylate, liquid crystal polyester, acetyl cellulose, cyclic polyolefin, saponified ethylene-vinyl acetate copolymer, polyvinyl chloride, etc., to about 1.0 to 6 times. The stretched film etc. which are obtained are mentioned. Among these, a polymer film obtained by uniaxially stretching or biaxially stretching polycarbonate or polyvinyl alcohol is preferable.

  As the retardation film, uniaxial retardation film, wide viewing angle retardation film, low photoelasticity retardation film, temperature compensation retardation film, LC film (rod-like liquid crystal twist orientation), WV film (disc-like liquid crystal tilt) Orientation), NH film (rod-like liquid crystal tilted orientation), VAC film (fully biaxially oriented retardation film), newVAC film (biaxially oriented retardation film), and the like.

Furthermore, what has bonded the board | substrate film (Protective Film) to the single side | surface or both surfaces of these optical films is used suitably as an optical film. Examples of the substrate film include an acrylic resin film different from the acrylic resin of the present invention, an acetyl cellulose film such as a cellulose triacetate film, a polyester resin film, an olefin resin film, a polycarbonate resin film, a polyether ether ketone resin film, and a polysulfone. Resin film etc. are mentioned. The substrate film, salicylate compounds, benzophenone compounds, benzotriazole compounds, triazine compounds, cyanoacrylate compounds, UV absorbers and nickel complex salt-based compound may be blended. Among the substrate films, acetylcellulose-based films are preferable.

The optical layered body of the present invention comprises an optical film with an adhesive and a glass substrate. Optical stack can usually be prepared by pasting a glass substrate pressure-sensitive adhesive layer of the optical film pressure-sensitive adhesive. Here, as a glass substrate, the glass substrate of a liquid crystal cell, the glass for glare-proof, the glass for sunglasses etc. are mentioned, for example. Among them, the adhesive layer of the optical film with adhesive (upper polarizing plate) is bonded to the glass substrate at the top of the liquid crystal cell, and another optical film with adhesive (lower polarizing plate) on the glass substrate at the lower part of the liquid crystal cell. ) Is preferably used because it can be used as a liquid crystal display device. Examples of the material for the glass substrate include soda lime glass, low alkali glass, and non-alkali glass.

Glass optical laminate of the present invention, even after peeling off the optical film pressure-sensitive adhesive therefrom, on the surface of the glass substrate which has been in contact with the adhesive layer, since such fogging and adhesive residue hardly occurs, peeled It is possible to easily re-adhere the optical film with pressure-sensitive adhesive to the substrate, that is, it has excellent reworkability.

Hereinafter, the present invention will be described more specifically with reference to examples. Incidentally, in the examples, "part" and "%" are by weight unless otherwise specified. The nonvolatile content was measured by a method according to JIS K-5407. Specifically, a representation of the pressure-sensitive adhesive solution any weight, 115 ° C. at an explosion-proof oven taken on a petri dish, 2 hours residual nonvolatile content by weight after drying at a rate against the weight of the first to the weighed solution It is. Weight average molecular weight measurement is more standard polystyrene using GPC apparatus, a sample concentration 5 mg / ml, the sample introduction amount 100Myuml, column as manufactured by Tosoh Corporation: two TSKgel G6000H _XL, two TSKgel G5000H _XL sequentially These were placed in series , and the reaction was carried out using tetrahydrofuran as an eluent under the conditions of a temperature of 40 ° C. and a flow rate of 1 ml / min.

<Examples of acrylic resin production>
(Polymerization example 1)
A reactor equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirrer was charged with 222 parts of ethyl acetate, the air inside the apparatus was replaced with nitrogen gas, and oxygen-free, then the internal temperature was raised to 75 ° C. Warm up. After addition of the total amount of azobisisobutyronitrile solution nitrile (hereinafter referred to as "AIBN") 0.55 parts was dissolved in 12.5 parts of ethyl acetate, while maintaining the internal temperature at 69-71 ° C., butyl A acrylic acid 36 Part, 44 parts of butyl methacrylate and 20 parts of methyl acrylate were dropped into the reaction system over 3 hours. Thereafter, the temperature was kept at 69 to 71 ° C. for 5 hours to complete the reaction. The resulting acrylic resin had a polystyrene equivalent weight average molecular weight of 100,000 by GPC.

(Polymerization Examples 2 to 7)
The reaction was completed in the same manner as in Polymerization Example 1 with the monomer composition shown in Table 1, and an acrylic resin having the weight average molecular weight (Mw) shown in Table 1 was obtained . The acrylic resins obtained in the above polymerization examples 1 to 7 correspond to the low molecular weight acrylic resin (1) defined in the present invention or the like.

(Polymerization Example 8)
A butyl acrylic acid 99 parts, was charged a mixed solution of 1.0 parts of A acrylic acid, after air in the apparatus was purged with nitrogen gas, while the oxygen-free, and the internal temperature was raised to 65 ℃, AIBN0. A total solution of 2 parts in 10 parts of ethyl acetate was added. Next , the temperature was kept at 65 ° C. for 6 hours, and then a solution in which 0.4 part of AIBN was dissolved in 20 parts of ethyl acetate was added dropwise over 1 hour, and the reaction was further continued for 2 hours to complete the polymerization. The resulting acrylic resin had a polystyrene equivalent weight average molecular weight of 1,150,000 and Mw / Mn of 8.0 by GPC.

(Polymerization Example 9)
The same reactor as in Polymerization Example 8, was charged 81.8 parts of acetone, 98.9 parts of A acrylic acid butyl Le, a mixed solution of 1.1 parts of A acrylic acid, air in the apparatus was purged with nitrogen gas, While not containing oxygen, the internal temperature was raised to 55 ° C., and then a total solution of 0.14 parts of AIBN dissolved in 10 parts of acetone was added. One hour after the addition of the initiator, the acetone solvent was continuously added at a rate of 17.3 parts by weight / hr so that the concentration of the acrylic resin excluding the monomer (hereinafter sometimes referred to as “ reaction concentration ” ) was 35 %. While being added to the reactor, the temperature was kept at 54 to 56 ° C. for 12 hours, and finally an ethyl acetate solvent was added to adjust the reaction concentration to 20%. The resulting acrylic resin had a weight average molecular weight of 1,200,000 and Mw / Mn of 3.9.

(Polymerization Example 10)
A reactor as in Polymerization Example 8, 80 parts of acetone, 95 parts of butyl A acrylic acid was charged a mixed solution of 5 parts of A acrylic acid, air in the apparatus was purged with nitrogen gas, while the oxygen-free, inner After raising the temperature to 55 ° C., a total amount of a solution prepared by dissolving 0.1 part of AIBN in 3 parts of acetone was added. Subsequently , the temperature was kept at 55 ° C. for 1 hour, and then acetone was added dropwise over 6 hours, followed by further reaction for 4 hours to complete the polymerization. The obtained acrylic resin had a polystyrene-reduced weight average molecular weight of 1,570,000 by GPC and Mw / Mn of 3.4.
Table 2 summarizes the monomer composition ratio, molecular weight, and molecular weight distribution of Polymerization Examples 8 to 10. The acrylic resins obtained in Polymerization Examples 8 to 10 correspond to the high molecular weight acrylic resin (2) defined in the present invention or the like.

Example 1
<Examples of adhesive production>
Acrylic resin (1) was mixed at a weight ratio of 40 parts (nonvolatile content) of acrylic resin obtained in Polymerization Example 3 and 60 parts of acrylic resin (nonvolatile content) obtained in Polymerization Example 9 as acrylic resin (2). An ethyl acetate solution of the resin composition was obtained. To 100 parts of the nonvolatile content of the resulting solution, 2 parts (nonvolatile content) of a tolylene diisocyanate adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) and a silane compound (trade name: Y11597, Toray Dow Corning) were mixed with 0.1 parts to obtain a pressure-sensitive adhesive of the present invention.

<Example of production of optical film with adhesive and optical laminate>
The pressure-sensitive adhesive thus obtained is applied to a release treatment surface of a release-treated polyethylene terephthalate film (product name: PET3811, manufactured by Lintec Corporation) so that the thickness after drying using an applicator is 25 μm. And dried at 90 ° C. for 1 minute to obtain a sheet-like pressure-sensitive adhesive. Then, using a polarization film as an optical film (film of three-layer structure sandwiching the both sides with triacetyl cellulose-based protective film but was stretched by adsorbing iodine on a polyvinyl alcohol), on the optical film was obtained in the The surfaces having the pressure-sensitive adhesive were bonded together by a laminator, and then aged for 10 days under the conditions of a temperature of 23 ° C. and a humidity of 65% to obtain an optical film with a pressure-sensitive adhesive provided with a pressure-sensitive adhesive layer. Subsequently, the optical film with pressure-sensitive adhesive was stuck to both surfaces of a glass substrate for liquid crystal cells (Corning Co., Ltd., 1737) so as to be crossed Nicol, thereby obtaining an optical laminate. These were evaluated and classified as follows , and the results are shown in Table 4.

<White Leakage of Optical Laminate>
After the optical layered body was stored at 80 ° C. and Dry for 96 hours, the expression state of white spots was evaluated in the following four stages.
A: No white spots are observed.
○: White spots are hardly noticeable.
Δ: White spots are slightly noticeable.
×: white spots is Me remarkably sure.

<Moisture and heat resistance of optical laminate>
The appearance change after storing the optical layered body at 60 ° C. and 90% RH for 96 hours was evaluated in the following four stages.
A: No change in appearance such as floating, peeling or foaming is observed.
○: Almost no change in appearance such as floating, peeling or foaming.
Δ: Appearance changes such as floating, peeling and foaming are slightly noticeable.
×: floating, peeling, change in appearance of the foam, and the Me remarkably sure.

<Heat resistance of optical laminate>
Appearance changes after the optical laminate was stored at 80 ° C. and Dry for 96 hours were evaluated in the following four stages.
A: No change in appearance such as floating, peeling or foaming is observed.
○: Almost no change in appearance such as floating, peeling or foaming.
Δ: Appearance changes such as floating, peeling and foaming are slightly noticeable.
×: floating, peeling, change in appearance of the foam, and the Me remarkably sure.

<Heat shock resistance (HS resistance) of optical laminate>
The process of heating the optical laminate to 60 ° C., lowering the temperature to −20 ° C., and further raising the temperature to 60 ° C. was defined as 1 cycle (1 hour), and the appearance change after 100 cycles of storage was evaluated in the following four stages.
A: No change in appearance such as floating, peeling or foaming is observed.
○: Almost no change in appearance such as floating, peeling or foaming.
Δ: Appearance changes such as floating, peeling and foaming are slightly noticeable.
×: floating, peeling, change in appearance of the foam, and the Me remarkably sure.

<Reworkability>
The reworkability was evaluated as follows. First, the optical film with an adhesive was prepared as a test piece of 25 mm × 150 mm. Next, this test piece is attached to a glass substrate for a liquid crystal cell by using an attaching device (“Lami Packer” manufactured by Fuji Plastic Machinery Co., Ltd.), and autoclaved at 50 ° C. and 5 kg / cm ² (490.3 kPa) for 20 minutes. Processed. Subsequently, after heat treatment at 70 ° C. for 2 hours and storage in an oven at 50 ° C. for 48 hours , this sticking test piece was placed at a rate of 300 mm / min in an atmosphere of 23 ° C. and 50% relative humidity. It peeled in the 180 degree direction, the state of the glass plate surface was observed, and it classified according to the following procedure .
◎: is not observed at all haze and adhesive residue on the surface of the glass plate.
A: Almost no fogging or the like is observed on the glass plate surface.
(Triangle | delta): Cloudiness etc. are recognized by the glass plate surface.
X: Adhesive residue is recognized on the glass plate surface.

(Examples 2-5 and Comparative Examples 1-7)
Acrylic resins (1) and (2) were mixed according to Example 1 at a weight ratio shown in Table 3 to obtain an ethyl acetate solution of the acrylic resin composition. The nonvolatile content 100 parts of the resulting solution, a crosslinking agent and a silane-compound the amount mixed shown in Tables 3, to obtain a pressure-sensitive adhesive of the present invention.
Table 3 Acrylic resin (1) and the mixing weight ratio of (2), the crosslinking agent species and amount, summarizes the silane compound classes and amounts. Table 4 summarizes the evaluation results.

Table 3 in M1, M3, X1, X2, Y1, Y3, Z1 and Z3 are below represents shown to sense, by [b] and [c] Each following formula (II) and (IV) can be obtained from these values [b] / ([b] + [b '] + [c]) can be obtained × 100. Note that [b ′] = 0 because no hydroxyl group-containing monomer was used in the acrylic resin (2).

[B] = ([X1 × Z1 × Y1 / 100] / M1) × 1000 / (X1 + X2) (II)
here,
X1: amount of the acrylic resin (1) (g) (nonvolatile content),
X2: The amount of the acrylic resin (2) (g) (nonvolatile content),
Y1: acrylic resin (1) charge of the hydroxyl group-containing monomers during production (%),
M1: Molecular weight of the hydroxyl group-containing monomer used in the production of the acrylic resin (1) ,
Z1: Number of hydroxyl groups per molecule of the hydroxyl group-containing monomer used during the production of the acrylic resin (1) .

[C] = ([X2 × Z3 × Y3 / 100] / M3) × 1000 / (X1 + X2) (IV)
here,
Y3: the acrylic resin (2) charge of the polar functional group-containing monomers during production (%),
M3: molecular weight of the polar functional group-containing monomer used in the production of the acrylic resin (2) ,
Z3: The number of polar functional groups per molecule of the polar functional group-containing monomer used during the production of the acrylic resin (2) .

The meanings of the names shown in the “type” column of the crosslinking agent and silane compound in Table 3 are as follows .
Coronate L: tolylene diisocyanate adduct manufactured by Nippon Polyurethane Industry Co., Ltd. "Coronate L".
D-110N: Mitsui Takeda Chemical Co., Ltd. of xylene diisocyanate adduct "Takenate D-110N".
Y11597: Dow Corning Toray Co., Ltd. of silane agent "Y11597".
X-41-1805: Shin-Etsu Chemical Co., Ltd. of silicone alkoxy oligomer "X-41-1805".
KBM403: manufactured by Shin-Etsu Chemical Co., Ltd. of the silane coupling agent "KBM403".

  The acrylic resin composition of this invention can be used as a main component of an adhesive suitable for optical laminated bodies, such as a TN liquid crystal cell (TFT), for example. Moreover, when the composition of this invention is used for the adhesive of a STN liquid crystal cell, the color nonuniformity of the optical laminated body obtained can be suppressed.

Claims (11)

The following formula (A):

(Wherein R ₁ represents a hydrogen atom or a methyl group,
R ₂ represents an alkyl group having 1 to 14 carbon atoms or an aralkyl group, and the hydrogen atom of the alkyl group of R ₂ or the hydrogen atom of the aralkyl group may be substituted with an alkoxy group having 1 to 10 carbon atoms. )
The structural unit (a) derived from (meth) acrylic acid ester represented by
0.1 to 10 mol% of structural unit (b) derived from a monomer containing in the molecule thereof at least one hydroxyl group and one olefinic double bond ,
A monomer containing in the molecule at least one polar functional group selected from the group consisting of a carboxyl 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 acrylic resin (1) to the structural unit (c) derived may contain 0 .01mol% or less as an optional component, a weight average molecular weight of 50,000 to 500,000, the
The structural units (a) as a main component, the structural unit (c) containing 0.5～8Mol%, may contain the structural units (b), the weight average molecular weight of 1,000,000～1,500,000 acrylic Resin (2)
100 parts by weight of the total of the acrylic resin (1) and (2), an acrylic resin composition containing 10 to 50 parts by weight of acrylic resin (1),
A hydroxyl group concentration [b] derived from the structural unit (b) contained in the acrylic resin (1), a hydroxyl group concentration [b ′] derived from the structural unit (b) contained in the acrylic resin (2), and an acrylic resin ( 2) The relationship with the polar functional group concentration [c] derived from the structural unit (c) contained in the formula (I) :
6 ≦ [b / (b + b ′ + c)] × 100 ≦ 50 (I)
(Here, the concentrations [b], [b ′] and [c]

Is a value corresponding to. )
An acrylic resin composition characterized by satisfying The acrylic resin composition according to 請 Motomeko 1 polar functional groups Ru der carboxyl group derived from the structural units contained in the acrylic resin (2) (c).   The adhesive which mix | blends the acrylic resin composition of Claim 1 or 2, and a crosslinking agent. Adhesive according to 請 Motomeko 3 crosslinker Ru der isocyanate compound. The cross-linking agent is at least one selected from the group consisting of tolylene diisocyanate, an adduct obtained by reacting tolylene diisocyanate with a polyol, one obtained by dimerizing tolylene diisocyanate, and one obtained by trimerizing tolylene diisocyanate. The pressure-sensitive adhesive according to claim 4 , which is a seed. Further adhesive according to any one of 請 Motomeko 3-5 you containing silane compound. The optical film with an adhesive formed by laminating | stacking the adhesive in any one of Claims 3-6 on both surfaces or one side of an optical film. Optical laminated film of the adhesive according to the optical film, polarizing film and / or the retardation film Der Ru請 Motomeko 7. Optical film, an optical film pressure-sensitive adhesive according to claim 7 or 8 further acetyl cellulose film is bonded as a protective film. Visco adhesive layer, an optical film with the pressure-sensitive adhesive according to yet claim 7 in which the release film is laminated. The optical laminated body by which the glass base material is laminated | stacked on the adhesive layer of the optical film with an adhesive in any one of Claims 7-9.