KR102375988B1 - Adhesive, bonded object and bonded object manufacturing method - Google Patents

Abstract

An object of the present invention is to provide an adhesive capable of obtaining an adhesive having high adhesive strength in adhesion between a film containing polyvinyl alcohol and a substrate, excellent in curing rate, and reduced warpage. The present invention is an adhesive for adhering a film containing polyvinyl alcohol to a substrate, and a (meth)acrylic polymer (X) having an active energy ray-curable group, and an active energy ray curability other than the (meth)acrylic polymer (X) The compound (Y) having a group is contained. Another aspect of the present invention is an adhesive for adhering a film containing polyvinyl alcohol to a substrate, wherein a polymer (X') having an active energy ray-curable group and a compound having an active energy ray-curable group other than the polymer (X') ( Y'), and the crosslinking density calculated|required from the storage elastic modulus of the rubbery flat region obtained by performing dynamic viscoelasticity measurement after hardening is 0.4 mol/L or more and 2 mol/L or less.

Description

An adhesive, an adhesive, and the manufacturing method of an adhesive {ADHESIVE, BONDED OBJECT AND BONDED OBJECT MANUFACTURING METHOD}

The present invention relates to an adhesive, an adhesive, and a method for producing the adhesive.

A film containing polyvinyl alcohol (hereinafter, sometimes referred to as "PVA film") is excellent in moisture permeability, heat retention, etc., and is used in various fields, such as a food packaging field, an agricultural field, and a medical field. In particular, the stretched PVA film is used as an optical film such as a polarizing film or retardation film.

As for the said polarizing film, a protective film is pasted together normally on the single side|surface or both surfaces via an aqueous solvent containing adhesive agent etc. As this protective film, transparent films, such as a triacetyl cellulose (TAC) film which has high moisture permeability, have been used, for example.

Recently, in order to improve the strength and durability of the protective film, it has been proposed to use a film other than the TAC film, such as a (meth)acrylic polymer film, a polyester film, or an alicyclic structure-containing polymer film, instead of a conventional TAC film. (For example, refer to Unexamined-Japanese-Patent No. 2008-241945 etc.). However, since these films have relatively low moisture permeability, when the above-mentioned water-based solvent-containing adhesive or the like is used, moisture in the adhesive is difficult to evaporate, it takes time to cure the adhesive, and there is a problem that the adhesive strength after curing is also low. .

Although active energy ray-curable compositions such as ultraviolet rays containing urethane (meth)acrylate obtained from a polyisocyanate compound and a hydroxyl group-containing (meth)acrylate compound have been developed (for example, International Publication No. 2010/123082) arc, etc.), there is room for improvement in adhesive strength.

Japanese Laid-Open Patent Publication No. 2008-241945 International Publication No. 2010/123082

The present invention has been made on the basis of the circumstances described above, and it is possible to obtain an adhesive having high adhesive strength, excellent curing rate, and reduced warpage in adhesion of a film containing polyvinyl alcohol to a substrate. An object of the present invention is to provide an adhesive, an adhesive obtained by using the adhesive, and a method for producing the adhesive.

The invention made to solve the above problem is an adhesive for adhering a film containing polyvinyl alcohol to a substrate, and a (meth)acrylic polymer (X) having an active energy ray-curable group, and a (meth)acrylic polymer (X) The compound (Y) which has other active energy ray-curable groups is contained (Hereinafter, the said adhesive agent may be called "adhesive agent (1)").

Another invention made in order to solve the above problem is an adhesive for adhering a film containing polyvinyl alcohol to a substrate, and a polymer (X') having an active energy ray-curable group, and an active agent other than the polymer (X') It contains the compound (Y') having an energy ray-curable group, and the crosslinking density obtained from the storage elastic modulus of the rubbery flat region obtained by measuring dynamic viscoelasticity after curing is 0.4 mol/L or more and 2 mol/L or less (hereinafter, the adhesive "Adhesive (2)" is sometimes called).

Another invention made in order to solve the above problem is an adhesive comprising a film containing polyvinyl alcohol, a substrate, and an adhesive layer disposed between the film and the substrate containing polyvinyl alcohol, the adhesive A layer is formed of the adhesive.

Further, another invention made to solve the above problems is a step of obtaining a laminate in which a film containing polyvinyl alcohol, the adhesive, and a substrate are arranged in this order, and after the step of obtaining the laminate, active energy ray It is a manufacturing method of an adhesive body provided with the process of irradiating to the said adhesive agent.

Since the adhesive (1) contains the (meth)acrylic polymer (X) and the compound (Y) having an active energy ray-curable group as described above, the affinity of the (meth)acrylic polymer (X) to the substrate; Adhesive strength between the film and the substrate containing polyvinyl alcohol by the adhesion of the compound (Y) to the film and the substrate containing polyvinyl alcohol, the interaction between the (meth)acrylic polymer (X) and the compound (Y), etc. It is excellent in a curing rate, and it is thought that the adhesive agent with which the curvature was reduced can be obtained.

In addition, since the adhesive (2) has excellent crosslinking density after curing within a specific range, it is excellent in balance between adhesion to a film and a substrate containing polyvinyl alcohol and strength of the cured product itself. It is thought that adhesive strength improves and the adhesive body with which the curvature was reduced can be obtained, and it is excellent also in a curing rate.

Moreover, since the adhesive bond layer is formed of the said adhesive agent as mentioned above, the said adhesive body is excellent in the adhesive strength of the film containing polyvinyl alcohol, and a base material, and curvature is reduced. Moreover, according to the manufacturing method of the said adhesive body, the said adhesive body can be manufactured easily and reliably.

Here, an "active energy ray-curable group" means a functional group which shows polymerizability by irradiation of an active energy ray, and includes the functional group which shows polymerizability through the action|action of an active energy ray polymerization initiator. "(meth)" such as "(meth)acrylic polymer" means to include both the notation with "meth" and the notation without "meth", and the notation with "meth" and without "meth" It indicates that it can be any of the notation. For example, "(meth)acrylic polymer" includes "methacrylic polymer" and "acrylic polymer", and indicates that either "methacrylic polymer" or "acrylic polymer" may be used. "Peel adhesive strength" is a value measured based on JISK6854-2 (1999).

As described above, the adhesive of the present invention has a high adhesive strength in adhesion between a film and a base material containing polyvinyl alcohol, has an excellent curing rate, and can obtain an adhesive with reduced warpage. Moreover, the adhesive body of this invention is excellent in the adhesive strength of the film containing polyvinyl alcohol, and a base material, and curvature is reduced. In addition, the method for producing an adhesive according to the present invention can easily and reliably produce the adhesive having excellent adhesive strength between a film containing polyvinyl alcohol and a substrate and having reduced warpage.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically an example of the adhesive agent of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of the adhesive agent of this invention, an adhesive agent, and the manufacturing method of an adhesive body are described in detail.

<Adhesive (1)>

The adhesive (1) is an adhesive for adhering a film containing polyvinyl alcohol to a substrate, and includes a (meth)acrylic polymer (X) having an active energy ray-curable group, and an activity other than the (meth)acrylic polymer (X) The compound (Y) which has an energy-beam curable group is contained.

[(meth)acrylic polymer (X)]

The (meth)acrylic polymer (X) has at least one active energy ray-curable group in the molecule. A film containing polyvinyl alcohol when the active energy ray-curable group of the (meth)acrylic polymer (X) is bonded to the compound (Y) and cured, or the (meth)acrylic polymer (X) is cured alone. It is thought that it is excellent in the adhesive strength of a base material and a hardening rate, and curvature of an adhesive agent can be reduced.

Examples of the active energy rays include electromagnetic waves such as ultraviolet rays, infrared rays, X-rays, and γ-rays, as well as electron beams, proton rays, and neutron rays. Among these, an ultraviolet-ray or an electron beam is preferable from a viewpoint of a curing rate, the availability of an irradiation apparatus, price, etc., and an ultraviolet-ray is more preferable.

The active energy ray-curable group is not particularly limited as long as it is a functional group that exhibits polymerizability by irradiation with active energy ray, for example, a group having an ethylenic double bond, a group having an oxirane ring, a group having an oxetane ring, thiol The group which has a group, the group which has a maleimide group, the group which has a hydrolysable silyl group, etc. are mentioned. As a minimum of carbon number of the said active energy ray-curable group, 1 is preferable and 2 is more preferable. On the other hand, as an upper limit of the said carbon number, 30 is preferable and 15 is more preferable. As group which has the said ethylenic double bond, group (group etc. which has a (meth)acryloyloxy group) which has group represented by following formula (1), for example; group having an allyl group; group having a vinyl group (such as group having a vinyl ether group); group having a 1,3-dienyl group; The group etc. which have a styryl group are mentioned.

[Formula 1]

In said formula (1), R< ¹ > represents a hydrogen atom or a C1-C20 hydrocarbon group.

As R ¹ , for example, a hydrogen atom, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 2-methylbutyl group, 3- Methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group, neopentyl group, n-hexyl group, 2-methylphen Alkyl groups, such as a tyl group, 3-methylpentyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, and n-eicosyl group; Cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group; Aryl groups, such as a phenyl group and a naphthyl group, etc. are mentioned. When R< ¹ > is a hydrocarbon group, as an upper limit of carbon number, 10 is preferable and 4 is more preferable.

Moreover, the C1-C20 hydrocarbon group represented by R< ¹ > may have a substituent. As this substituent, what is necessary is just what does not impair the active energy ray sclerosis|hardenability of an active energy ray-curable group, For example, Alkoxy groups, such as a methoxy group, an ethoxy group, an isopropoxy group, t-butoxy group; Halogen atoms, such as a chlorine atom and a bromine atom, etc. are mentioned.

R ¹ is preferably a hydrogen atom or a methyl group from the viewpoint of being excellent in the easiness of production or curing rate of the (meth)acrylic polymer (X).

Among the active energy ray-curable groups, at least one selected from the group consisting of a group having an ethylenic double bond, a group having an oxirane ring, and a group having an oxetane ring is preferable from the viewpoint of excellent handleability and reactivity, At least one selected from the group consisting of a group having a group represented by the formula (1), a group having an oxirane ring, and a group having an oxetane ring is more preferable, and a group having a group represented by the formula (1) is still more preferable .

Although the group in particular which has group represented by the said Formula (1) is not restrict|limited, From the point which the effect of this invention is exhibited more notably, group represented by following formula (2) is preferable.

[Formula 2]

In the formula (2), R ² and R ³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, X ¹ represents an oxygen atom, a sulfur atom or -NR ⁴ -, R ⁴ is a hydrogen atom or A C1-C6 hydrocarbon group is shown, and n shows the integer of 1-20.

In addition, the definition and description of R< ¹ > in said Formula (2) are the same as that of said Formula (1).

As R ² and R ³ , for example, a hydrogen atom, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 2-methylbutyl group group, 3-methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group, neopentyl group, n-hexyl group, Alkyl groups, such as a 2-methylpentyl group and 3-methylpentyl group; Cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; Aryl groups, such as a phenyl group, etc. are mentioned.

Moreover, the C1-C6 hydrocarbon group represented by R< ² > and R< ³ > may have a substituent. As this substituent, what is necessary is just what does not impair the active energy ray sclerosis|hardenability of an active energy ray-curable group, For example, Alkoxy groups, such as a methoxy group, an ethoxy group, an isopropoxy group, t-butoxy group; Halogen atoms, such as a chlorine atom and a bromine atom, etc. are mentioned.

R ² and R ³ are each preferably a methyl group or an ethyl group from the viewpoint of being excellent in the easiness of production and curing rate of the (meth)acrylic polymer (X).

Examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 2- Methylbutyl group, 3-methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group, neopentyl group, n-hexyl group Alkyl groups, such as a real group, 2-methylpentyl group, and 3-methylpentyl group; Cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; Aryl groups, such as a phenyl group, etc. are mentioned.

Moreover, the C1-C6 hydrocarbon group represented by ^R4 may have a substituent. As this substituent, what is necessary is just what does not impair the active energy ray sclerosis|hardenability of an active energy ray-curable group, For example, Alkoxy groups, such as a methoxy group, an ethoxy group, an isopropoxy group, t-butoxy group; Halogen atoms, such as a chlorine atom and a bromine atom, etc. are mentioned.

R ⁴ is preferably a methyl group or an ethyl group from the viewpoint of being excellent in the ease of production or curing rate of the (meth)acrylic polymer (X).

X ¹ is preferably an oxygen atom or -NR ⁴ -, more preferably an oxygen atom, from the viewpoint of being excellent in the ease of production and curing rate of the (meth)acrylic polymer (X).

The lower limit of n is preferably 2, while the upper limit of n is preferably 10, and more preferably 5, from the viewpoints of ease of production of the (meth)acrylic polymer (X) and excellent curing rate.

The (meth)acrylic polymer (X) is a polymer mainly containing a structural unit derived from a (meth)acrylic monomer, and may be a homopolymer or a copolymer. As a (meth)acrylic-type monomer, what has a partial structure represented, for example by following formula (4) is mentioned. Here, in the (meth)acrylic polymer (X), part or all of the structural unit derived from the (meth)acrylic monomer having a partial structure represented by the following formula (4) has an active energy ray-curable group, and consequently active energy ray Although it may have a curable group, even when some or all of the structural units derived from the (meth)acrylic-type monomer which has a partial structure represented by following formula (4) do not have an active energy ray-curable group, the terminal of the said polymer and/or By making the side chain have an active energy ray-curable group, it can be set as the (meth)acrylic-type polymer (X) which has an active energy ray-curable group as a result.

[Formula 3]

In the formula (4), R ⁷ represents a hydrogen atom or a methyl group, X ³ represents an oxygen atom, a sulfur atom or -NR ⁸ -, and R ⁸ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

As R ⁷ , a methyl group is preferable.

Examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ⁸ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 2- Methylbutyl group, 3-methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group, neopentyl group, n-hexyl group Alkyl groups, such as a real group, 2-methylpentyl group, and 3-methylpentyl group; Cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; Aryl groups, such as a phenyl group, etc. are mentioned.

Moreover, the C1-C6 hydrocarbon group represented by R< ⁸ > may have a substituent. As this substituent, what is necessary is just what does not impair the active energy ray sclerosis|hardenability of an active energy ray-curable group, For example, Alkoxy groups, such as a methoxy group, an ethoxy group, an isopropoxy group, t-butoxy group; Halogen atoms, such as a chlorine atom and a bromine atom, etc. are mentioned.

R ⁸ is preferably a methyl group or an ethyl group from the viewpoint of being excellent in the easiness of production and curing rate of the (meth)acrylic polymer (X).

X ³ is preferably an oxygen atom or -NR ⁸ -, more preferably an oxygen atom, from the viewpoint of being excellent in the ease of production and curing rate of the (meth)acrylic polymer (X).

As a specific example of the said (meth)acrylic-type monomer in the case where X< ³ > is an oxygen atom, the compound etc. which have an active energy ray-curable group and a (meth)acryloyloxy group other than that are mentioned, for example. In addition to that, for example, (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate n-propyl, (meth) acrylate isopropyl, (meth) acrylate n-butyl, (meth) acrylate t-butyl, (meth)acrylic acid cyclohexyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid isobornyl, (meth)acrylic acid lauryl, (meth)acrylic acid dodecyl, (meth)acrylic acid trimethoxysilylpropyl, (meth)acrylic acid ) Acrylic acid N,N-dimethylaminoethyl, (meth)acrylic acid N,N-diethylaminoethyl, (meth)acrylic acid 2-methoxyethyl, (meth)acrylic acid phenyl, (meth)acrylic acid naphthyl, (meth)acrylic acid 2-(trimethylsilyloxy)ethyl, (meth)acrylic acid 3-(trimethylsilyloxy)propyl, etc. are mentioned.

As the lower limit of the ratio of the number of moles of structural units derived from the (meth)acrylic monomer to the number of moles of all the structural units constituting the (meth)acrylic polymer (X), 30 mol% is preferable, and 50 mol% is more It is preferable, 80 mol% is more preferable, 95 mol% is especially preferable, and 100 mol% may be sufficient as the said ratio.

Moreover, as a lower limit of the ratio of the number of moles of an active energy ray-curable group with respect to the number of moles of all the structural units constituting the (meth)acrylic polymer (X), 0.3 mol% is preferable, and 1 mol% is more preferable, 2 mol% is more preferable. On the other hand, as an upper limit of the said ratio, 90 mol% is preferable, 30 mol% is more preferable, 15 mol% is more preferable, and 10 mol% is especially preferable. When the ratio of the number of moles of active energy ray-curable groups to the number of moles of all structural units constituting the (meth)acrylic polymer (X) is within the above range, the adhesive (2) described later is easily obtained, and the adhesive strength is further improved, and an adhesive capable of further reducing warpage is easily obtained.

When (meth)acrylic-type polymer (X) is a copolymer, as (meth)acrylic-type polymer (X), a random copolymer, a block copolymer, etc. are mentioned, for example. As a random copolymer, the (meth)acrylic-type polymer (acrylic resin (meth)acrylate etc.) etc. which have a (meth)acryloyloxy group in the terminal and/or a side chain are mentioned, for example. As the (meth)acrylic polymer (X), in particular, an adhesive having a further reduced curvature can be obtained, and the effect of the present invention is more notably exhibited, so a block copolymer is preferable, having an active energy ray-curable group ( The block copolymer which has a meth)acrylic-type polymer block (A) and the (meth)acrylic-type polymer block (B) which does not have an active energy ray-curable group substantially is more preferable. As described above, since the (meth)acrylic polymer (X) has a (meth)acrylic polymer block (A) and a (meth)acrylic polymer block (B), the adhesive has improved followability to unevenness on the surface of the substrate, It is thought that curvature is further reduced by the anchor effect etc., and adhesive strength improves more.

((meth)acrylic polymer block (A))

The (meth)acrylic polymer block (A) is a (meth)acrylic polymer block having an active energy ray-curable group. The lower limit of the ratio of the number of moles of structural units derived from the (meth)acrylic monomer to the number of moles of all the structural units constituting the (meth)acrylic polymer block (A) is preferably 30 mol%, and 50 mol% is More preferably, 80 mol% is more preferable, 95 mol% is especially preferable, and 100 mol% may be sufficient as the said ratio.

The (meth)acrylic polymer block (A) is formed by addition polymerization of an ethylenic double bond of a vinyl-based compound having an ethylenic double bond different from an active energy ray-curable group (hereinafter referred to as “active energy ray-curable monomer”) It is preferable to have a structural unit which becomes

As an active energy ray-curable monomer, the compound represented, for example by following formula (5) is mentioned preferably. The compound represented by this formula (5) may be used individually by 1 type, and may use 2 or more types together.

[Formula 4]

In the formula (5), the definitions and explanations for each of R ¹ , R ² , R ³ , X ¹ and n are the same as those of the formulas (1) and (2). Moreover, in said Formula (5), although two or more R< ¹ > may mutually be same or different, the same thing is preferable for the ease of manufacture of the compound represented by the said Formula (5), etc.

As the active energy ray-curable monomer, in addition to the compound represented by the formula (5), for example, a group having an oxirane ring and a vinyl compound having an ethylenic double bond, a group having an oxetane ring, and an ethylenic double bond It may be a vinyl-type compound which has. An active energy ray-curable monomer may be used individually by 1 type, and may use 2 or more types together.

As a lower limit of the content rate of the structural unit derived from an active energy ray-curable monomer with respect to all the structural units which form the (meth)acrylic-type polymer block (A), 5 mol% is preferable, 10 mol% is more preferable, 20 mol% is more preferable. On the other hand, as an upper limit of the said content rate, 90 mol% is preferable and 70 mol% is more preferable, However, The structural unit derived from the (meth)acrylic-type monomer which the (meth)acrylic-type polymer block (A) has is active energy ray-curable. When formed from a monomer, 100 mol% may be sufficient as the upper limit of the said content rate.

The (meth)acrylic polymer block (A) may have a structural unit derived from mono(meth)acrylic acid ester as a structural unit derived from a (meth)acrylic monomer other than a structural unit derived from an active energy ray-curable monomer.

Examples of the mono (meth) acrylic acid ester include (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylic acid n-propyl, (meth) acrylate isopropyl, (meth) acrylic acid n-butyl, (meth) ) Acrylic acid t-butyl, (meth)acrylic acid cyclohexyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid isobornyl, (meth)acrylic acid lauryl, (meth)acrylic acid dodecyl, (meth)acrylic acid trime Toxysilylpropyl, (meth)acrylic acid N,N-dimethylaminoethyl, (meth)acrylic acid N,N-diethylaminoethyl, (meth)acrylic acid 2-methoxyethyl, (meth)acrylic acid phenyl, (meth)acrylic acid naph ethyl, (meth)acrylic acid 2-(trimethylsilyloxy)ethyl, (meth)acrylic acid 3-(trimethylsilyloxy)propyl, and the like. Among them, an alkyl group having 5 or less carbon atoms, such as (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, etc. A (meth)acrylic acid alkyl ester having Moreover, as mono(meth)acrylic acid ester, monomethacrylic acid ester is preferable. These mono(meth)acrylic acid esters may be used individually by 1 type, and may use 2 or more types together.

As an upper limit of the content rate of the structural unit derived from the said mono(meth)acrylic acid ester with respect to all the structural units which form the (meth)acrylic-type polymer block (A), 95 mol% is preferable, and 90 mol% is more preferable, , 80 mol% is more preferable. On the other hand, as a lower limit of the said content rate, 0 mol% is preferable, 20 mol% is more preferable, and its 30 mol% is still more preferable.

The (meth)acrylic polymer block (A) is a structural unit derived from a (meth)acrylic monomer or other structural unit derived from other monomers other than the active energy ray-curable monomer and mono (meth)acrylic acid ester. You may have a structural unit.

As said other monomer, For example, (alpha)-alkoxy acrylic acid ester, such as (alpha)-methyl methoxyacrylate and (alpha)-ethoxy methyl acrylate; Crotonic acid esters, such as a methyl crotonate and an ethyl crotonate; 3-alkoxyacrylic acid esters, such as 3-methoxyacrylic acid ester; acrylamides such as N-isopropylacrylamide, N-t-butylacrylamide, N,N-dimethylacrylamide, and N,N-diethylacrylamide; methacrylamides such as N-isopropyl methacrylamide, N-t-butyl methacrylamide, N,N-dimethyl methacrylamide, and N,N-diethyl methacrylamide; 2-phenyl methyl acrylate, 2-phenyl acrylate, n-butyl 2-bromoacrylate, 2-bromomethyl methyl acrylate, 2-bromomethyl ethyl acrylate, methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone , ethyl isopropenyl ketone, and the like. These other monomers may be used individually by 1 type, and may use 2 or more types together.

As an upper limit of the content rate of the structural unit derived from the said other monomer with respect to all the structural units which form the (meth)acrylic-type polymer block (A), 10 mol% is preferable and 5 mol% is more preferable.

Although there is no restriction|limiting in particular in the number average molecular weight (Mn) of the (meth)acrylic-type polymer block (A), From the point of handleability, fluidity|liquidity, mechanical properties, etc. of the (meth)acrylic-type polymer (X) obtained, the lower limit of the said Mn is , 500 are preferable, and 1,000 are more preferable. On the other hand, as an upper limit of the said Mn, 1,000,000 is preferable and 300,000 is more preferable.

((meth)acrylic polymer block (B))

A (meth)acrylic-type polymer block (B) is a (meth)acrylic-type polymer block which does not have an active energy ray-curable group substantially. Here, as an example in the case of not having an active energy ray-curable group substantially, the content rate of the structural unit derived from an active energy ray-curable monomer with respect to all the structural units which form the (meth)acrylic-type polymer block (B) is, for example, Less than 5 mol%, less than 3 mol%, less than 1 mol%, less than 0.5 mol%, furthermore, the case where it is 0 mol% etc. are mentioned. The lower limit of the ratio of the number of moles of structural units derived from the (meth)acrylic monomer to the number of moles of all the structural units constituting the (meth)acrylic polymer block (B) is preferably 30 mol%, and 50 mol% is More preferably, 80 mol% is more preferable, 95 mol% is especially preferable, and 100 mol% may be sufficient as the said ratio.

The (meth)acrylic polymer block (B) may have a structural unit derived from (meth)acrylic acid ester as a structural unit derived from a (meth)acrylic monomer. As such (meth)acrylic acid ester, monoacrylic acid ester, monomethacrylic acid ester, etc. are mentioned, for example.

Examples of the monoacrylic acid ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, Lauryl acrylate, dodecyl acrylate, trimethoxysilylpropyl acrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, 2-methoxyethyl acrylate, phenyl acrylate, naphthyl acrylate, acrylic acid 2 -(trimethylsilyloxy)ethyl, acrylic acid 3-(trimethylsilyloxy)propyl, etc. are mentioned.

Examples of the monomethacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, methacrylate Cyclohexyl acrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, lauryl methacrylate, dodecyl methacrylate, trimethoxysilylpropyl methacrylate, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, 2-methoxyethyl methacrylate, phenyl methacrylate, naphthyl methacrylate, 2-(trimethylsilyloxy)ethyl methacrylate, 3-(methacrylic acid) trimethylsilyloxy) propyl and the like.

The (meth)acrylic acid ester is preferably an acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms, and an methacrylic acid alkyl ester having an alkyl group having 6 or more carbon atoms, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, Lauryl acrylate, dodecyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and dodecyl methacrylate are more preferable. In addition, these (meth)acrylic acid ester may be used individually by 1 type, and may use 2 or more types together.

As a lower limit of the content rate of the structural unit derived from the said (meth)acrylic acid ester with respect to all the structural units which form the (meth)acrylic-type polymer block (B), 90 mol% is preferable and 95 mol% is more preferable.

The (meth)acrylic polymer block (B) may have a structural unit derived from another monomer other than the (meth)acrylic acid ester as a structural unit derived from a (meth)acrylic monomer or as a structural unit other than that. As another monomer, alpha-alkoxy acrylic acid ester, such as (alpha)-methyl methoxyacrylate and (alpha)-ethoxy methyl acrylate; Crotonic acid esters, such as a methyl crotonate and an ethyl crotonate; 3-alkoxyacrylic acid esters, such as 3-methoxyacrylic acid ester; acrylamides such as N-isopropylacrylamide, N-t-butylacrylamide, N,N-dimethylacrylamide, and N,N-diethylacrylamide; methacrylamides such as N-isopropyl methacrylamide, N-t-butyl methacrylamide, N,N-dimethyl methacrylamide, and N,N-diethyl methacrylamide; Methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone, ethyl isopropenyl ketone, etc. are mentioned. These other monomers may be used individually by 1 type, and may use 2 or more types together.

As an upper limit of the content rate of the structural unit derived from the said other monomer with respect to all the structural units which form the (meth)acrylic-type polymer block (B), 10 mol% is preferable and 5 mol% is more preferable.

Although there is no restriction|limiting in particular in the number average molecular weight (Mn) of the (meth)acrylic-type polymer block (B), From the point of handleability, fluidity|liquidity, mechanical properties, etc. of the (meth)acrylic-type polymer (X) obtained, the lower limit of the said Mn is , 3,000 are preferable, and 5,000 are more preferable. On the other hand, as an upper limit of the said Mn, 5,000,000 is preferable and 1,000,000 is more preferable.

The (meth)acrylic polymer (X) is preferably a block copolymer in which at least one (meth)acrylic polymer block (A) and at least one (meth)acrylic polymer block (B) are bonded to each other. When the (meth)acrylic polymer (X) is a block copolymer having a (meth)acrylic polymer block (A) and a (meth)acrylic polymer block (B), the number and bonding order of each polymer block are not particularly limited, but ( From the viewpoint of the ease of production of the meth)acrylic polymer (X), a diblock copolymer in which one (meth)acrylic polymer block (A) and one (meth)acrylic polymer block (B) are bonded and one (meth)acrylic polymer A triblock copolymer in which one (meth)acrylic polymer block (A) is bonded to both ends of the polymer block (B) is preferable. As described above, since the blocks at both ends of the (meth)acrylic polymer (X) are the (meth)acrylic polymer blocks (A) having an active energy ray-curable group, these (meth)acrylic polymer blocks (A) are the polymerization of the adhesive. Since they interact during curing to form a network structure, the toughness after curing of the adhesive is improved, and as a result, it is considered that the adhesive strength is further improved. Moreover, it is thought that the curvature of the adhesive agent obtained is reduced more when a (meth)acrylic-type polymer block (B) exists between (meth)acrylic-type polymer blocks (A).

When the (meth)acrylic polymer (X) is a block copolymer having a (meth)acrylic polymer block (A) and a (meth)acrylic polymer block (B), a (meth)acrylic polymer block (A) and a (meth)acrylic polymer As a structural ratio of a block (B), 5:95 or more and 90:10 or less are preferable in mass ratio. When the ratio of the (meth)acrylic polymer block (A) to the total of the (meth)acrylic polymer block (A) and the (meth)acrylic polymer block (B) is 5 mass% or more, the curing rate and curing by active energy rays The later adhesive strength becomes favorable. On the other hand, when the ratio of the (meth)acrylic polymer block (B) is 10 mass % or more, the viscoelasticity after curing of the adhesive is good.

Although there is no particular limitation on the number average molecular weight (Mn) of the (meth)acrylic polymer (X) as a whole, from the viewpoints of handling, fluidity, and mechanical properties of the (meth)acrylic polymer (X), the lower limit of Mn is, 4,000 is preferable, 5,000 is more preferable, and 7,000 is more preferable. On the other hand, the upper limit of Mn is preferably 7,000,000, more preferably 3,000,000, and still more preferably 2,000,000.

Although there is no restriction|limiting in particular in the molecular weight distribution (Mw/Mn) of the whole (meth)acrylic-type polymer (X), As an upper limit of the said Mw/Mn, 2.0 is preferable, 1.5 is more preferable, and 1.2 is still more preferable. Thus, by making the said Mw/Mn below the said upper limit, the adhesive strength and hardening rate of the said adhesive agent can be raised more.

As a lower limit of the content rate of the (meth)acrylic polymer (X) in the said adhesive agent (1), 1 mass % is preferable, 3 mass % is more preferable, 5 mass % is still more preferable, 10 mass % is It is especially preferable, and it is good also considering the said content rate as 15 mass % or more. On the other hand, as an upper limit of the said content rate, 90 mass % is preferable, 70 mass % is more preferable, and 50 mass % is especially preferable. When the said content is more than the said lower limit, mechanical properties, such as adhesive strength of the said adhesive agent, improve more, and the adhesive body with which curvature was further reduced can be obtained. On the other hand, when the said content rate is below the said upper limit, the viscosity of the said adhesive agent can be maintained moderately, and handleability improves.

(Method for producing (meth)acrylic polymer (X))

There is no restriction|limiting in particular in the manufacturing method of the (meth)acrylic-type polymer (X), For example, it can obtain by superposing|polymerizing the said active energy ray-curable monomer with another (meth)acrylic-type monomer as needed. When the (meth)acrylic polymer (X) is a block copolymer having a (meth)acrylic polymer block (A) and a (meth)acrylic polymer block (B), it is a monomer containing an active energy ray-curable monomer and (meth) A first polymerization step of anionically polymerizing a monomer containing an acrylic monomer in the presence of an organolithium compound, a tertiary organoaluminum compound and a Lewis base, and a monomer substantially free of an active energy ray-curable monomer after the first polymerization step Furthermore, a production method comprising a second polymerization step of adding a monomer containing a (meth)acrylic monomer and anionic polymerization is preferred. According to this manufacturing method, the (meth)acrylic-type polymer (X) made into the objective can be manufactured efficiently. Moreover, in this case, you may further provide the 3rd polymerization process of adding a monomer which is a monomer containing an active energy ray-curable monomer and also contains a (meth)acrylic-type monomer after a 2nd polymerization process, and carries out anion polymerization.

(1st polymerization process)

In a 1st polymerization process, the monomer which is a monomer containing an active energy ray-curable monomer and contains a (meth)acrylic-type monomer is anionic-polymerized in presence of an organolithium compound, a tertiary organoaluminum compound, and a Lewis base. The monomer used in the 1st polymerization process may contain the active energy ray-curable monomer as a (meth)acrylic-type monomer, and may contain the (meth)acrylic-type monomer other than an active energy ray-curable monomer. As for the content rate of the active energy ray-curable monomer in the monomer used in a 1st polymerization process, 5 mol% or more and 100 mol% or less are preferable.

1st polymerization process WHEREIN: When using the compound represented by said Formula (5) as an active energy ray-curable monomer, at least one of ^R2 and R3, Preferably both of ^R2 and R3 have ¹ to C1- ^C It is preferable that it is a hydrocarbon group of 6. As described above, since R ² and/or R ³ is a hydrocarbon group having 1 to 6 carbon atoms, the ethylenic double on the side other than the -OCO-CR ¹ =CH ₂ group directly bonded to the carbon atom to which R ² and R ³ are bonded. The bonds are selectively polymerized, while polymerization of the -OCO-CR ¹ =CH ₂ group directly bound to the carbon atom to which R ² and R ³ is bound is suppressed and remains in the side chain of the (meth)acrylic polymer (X). It is preferable because The number of active energy ray-curable monomers used in a 1st polymerization process may be one, and 2 or more types may be sufficient as them.

The monomer used in the 1st polymerization process may contain mono(meth)acrylic acid ester as a (meth)acrylic-type monomer other than an active energy ray-curable monomer. As this mono(meth)acrylic acid ester, the thing similar to the mono(meth)acrylic acid ester illustrated in the said (meth)acrylic-type polymer block (A) can be used, for example. Mono (meth)acrylic acid ester may use only 1 type, and may use 2 or more types.

The upper limit of the ratio of the active energy ray-curable monomer to the total of the active energy ray-curable monomer and the mono(meth)acrylic acid ester in the monomer used in the first polymerization step is preferably 100 mol%, and 80 mol% is More preferably, 70 mol% is still more preferable. On the other hand, as a lower limit of the said ratio, 5 mol% is preferable, 10 mol% is more preferable, and its 20 mol% is still more preferable. By making the said ratio into the said range, the rate of anionic polymerization in a 1st polymerization process, the curing rate of the said adhesive agent, and the adhesive strength after hardening improve more.

In a 1st polymerization process, you may superpose|polymerize other monomers other than an active energy ray-curable monomer and mono(meth)acrylic acid ester as a (meth)acrylic-type monomer or as a monomer other than that. As said other monomer, the thing similar to the other monomer illustrated in the said (meth)acrylic-type polymer block (A) can be used, for example. As for another monomer, only 1 type may be used and 2 or more types may be used for it.

1st polymerization process WHEREIN: As an upper limit of the usage-amount of the other monomer with respect to the sum total of an active energy ray-curable monomer, mono(meth)acrylic acid ester, and another monomer, 10 mol% is preferable and 5 mol% is more preferable. When the said usage-amount is below the said upper limit, the curing rate of the said adhesive agent and the adhesive strength after hardening improve more.

The monomers (active energy ray-curable monomer and optional component mono (meth) acrylic acid ester and other monomers) used in the first polymerization step are dried in advance under an inert gas atmosphere from the viewpoint of smoothly proceeding anionic polymerization. it is preferable As a processing agent used for this drying process, dehydrating agents or drying agents, such as calcium hydride, molecular sieves, and activated alumina, are mentioned, for example.

The organolithium compound acts as an anionic polymerization initiator. As an organolithium compound, the C3-C30 organolithium compound which has a structure which has a carbon atom as an anion center is mentioned, for example. Examples of such an organolithium compound include t-butyllithium, 2,2-dimethylpropyllithium, 1,1-diphenylhexyllithium, 1,1-diphenyl-3-methylpentyllithium, and ethyl α-lithium. Oisobutylate, Butyl α-Lithioisobutylate, Methyl α-Lithioisobutylate, Isopropyllithium, sec-butyllithium, 1-methylbutyllithium, 2-ethylpropyllithium, 1-methylpentyllithium, cyclohexyllithium , diphenylmethyllithium, α-methylbenzyllithium, methyllithium, n-propyllithium, n-butyllithium, n-pentyllithium, and n-hexyllithium. These organolithium compounds may be used individually by 1 type, and may use 2 or more types together.

Examples of the organolithium compound include isopropyllithium, sec-butyllithium, 1-methylbutyllithium, 1-methylpentyllithium, cyclohexyllithium, diphenylmethyllithium, α- Organolithium compounds having 4 to 15 carbon atoms and the like having a secondary carbon atom as an anion center, such as methylbenzyllithium, are preferable, and sec-butyllithium is more preferable.

The amount of the organolithium compound to be used relative to the total amount of the monomers (active energy ray-curable monomer and optional component mono(meth)acrylic acid ester and other monomers) used in the first polymerization step is preferably 0.0001 mole times or more and 0.3 mole times or less. By making the usage-amount of an organolithium compound into the said range, the target (meth)acrylic-type polymer (X) can be manufactured smoothly.

As said tertiary organoaluminum compound, the compound containing the structure represented by following formula (6) is preferable, and the compound represented by following formula (6-1) or (6-2) is more preferable. By using these compounds as a tertiary organoaluminum compound, polymerization rate, polymerization initiation efficiency, stability of polymerization terminal anion, etc. can be improved. These tertiary organoaluminum compounds may use only 1 type, and may use 2 or more types.

[Formula 5]

In the formula (6), Ar represents an aromatic ring.

[Formula 6]

In the formula (6-1), R ⁹ represents a monovalent saturated hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group, an aryloxy group or a N,N-2 substituted amino group, and R ¹⁰ and R ¹¹ are each independently An aryloxy group or an arylenedioxy group by bonding to each other.

[Formula 7]

In the formula (6-2), R ¹² represents an aryloxy group, and R ¹³ and R ¹⁴ each independently represent a monovalent saturated hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group, or a N,N-2 substituted amino group. .

Examples of the aryloxy group represented by R ⁹ , R ¹⁰ , R ¹¹ and R ¹² include phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, 2,6-dimethylphenoxy group, 2,4-di- t-butylphenoxy group, 2,6-di-t-butylphenoxy group, 2,6-di-t-butyl-4-methylphenoxy group, 2,6-di-t-butyl-4-ethylphenoxy group, 2,6-diphenylphenoxy group, 1-naphthoxy group, 2-naphthoxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 7-methoxy-2-naphthoxy group, etc. are mentioned.

Examples of the arylenedioxy group represented by R ¹⁰ and R ¹¹ bonded to each other include 2,2'-biphenol, 2,2'-methylenebisphenol, and 2,2'-methylenebis(4-methyl-6-t). -Butylphenol), (R)-(+)-1,1'-bi-2-naphthol, (S)-(-)-1,1'-bi-2-naphthol, etc. from two phenolic hydroxyl groups A group from which a hydrogen atom has been removed is exemplified.

Examples of the monovalent saturated hydrocarbon group represented by R ⁹ , R ¹³ and R ¹⁴ include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl group. Alkyl groups, such as group, 2-methylbutyl group, 3-methylbutyl group, n-octyl group, and 2-ethylhexyl group; Cycloalkyl groups, such as a cyclohexyl group, etc. are mentioned.

Examples of the monovalent aromatic hydrocarbon group represented by R ⁹ , R ¹³ and R ¹⁴ include an aryl group such as a phenyl group; Aralkyl groups, such as a benzyl group, etc. are mentioned.

Examples of the alkoxy group represented by R ⁹ , R ¹³ and R ¹⁴ include a methoxy group, an ethoxy group, an isopropoxy group, and a t-butoxy group.

Examples of the N,N-2 substituted amino group represented by R ⁹ , R ¹³ and R ¹⁴ include dialkylamino groups such as dimethylamino group, diethylamino group, and diisopropylamino group; A bis(trimethylsilyl)amino group etc. are mentioned.

One or more hydrogen atoms that R ⁹ to R ¹⁴ have may be substituted with a substituent. As such a substituent, For example, Alkoxy groups, such as a methoxy group, an ethoxy group, an isopropoxy group, and t-butoxy group; and halogen atoms such as chlorine and bromine.

Examples of the tertiary organoaluminum compound represented by the formula (6-1) include methylbis(2,6-di-t-butyl-4-methylphenoxy)aluminum and ethylbis(2,6-di). -t-Butyl-4-methylphenoxy)aluminum, ethylbis(2,6-di-t-butylphenoxy)aluminum, ethyl[2,2'-methylenebis(4-methyl-6-t-butylphenoxy) C)]aluminum, isobutylbis(2,6-di-t-butyl-4-methylphenoxy)aluminum, isobutylbis(2,6-di-t-butylphenoxy)aluminum, isobutyl[2, 2'-methylenebis(4-methyl-6-t-butylphenoxy)]aluminum, n-octylbis(2,6-di-t-butyl-4-methylphenoxy)aluminum, n-octylbis(2 ,6-di-t-butylphenoxy)aluminum, n-octyl[2,2'-methylenebis(4-methyl-6-t-butylphenoxy)]aluminum, methoxybis(2,6-di- t-Butyl-4-methylphenoxy)aluminum, methoxybis(2,6-di-t-butylphenoxy)aluminum, methoxy[2,2'-methylenebis(4-methyl-6-t-butyl) phenoxy)]aluminum, ethoxybis(2,6-di-t-butyl-4-methylphenoxy)aluminum, ethoxybis(2,6-di-t-butylphenoxy)aluminum, ethoxy[2 ,2'-methylenebis(4-methyl-6-t-butylphenoxy)]aluminum, isopropoxybis(2,6-di-t-butyl-4-methylphenoxy)aluminum, isopropoxybis( 2,6-di-t-butylphenoxy)aluminum, isopropoxy[2,2'-methylenebis(4-methyl-6-t-butylphenoxy)]aluminum, t-butoxybis(2,6 -di-t-butyl-4-methylphenoxy)aluminum, t-butoxybis(2,6-di-t-butylphenoxy)aluminum, t-butoxy[2,2'-methylenebis(4- methyl-6-t-butylphenoxy)]aluminum, tris(2,6-di-t-butyl-4-methylphenoxy)aluminum, tris(2,6-diphenylphenoxy)aluminum, etc. are mentioned. .

Among these, the tertiary organoaluminum compound represented by the formula (6-1) is isobutylbis(2,6- Di-t-butyl-4-methylphenoxy)aluminum, isobutylbis(2,6-di-t-butylphenoxy)aluminum, or isobutyl[2,2'-methylenebis(4-methyl-6-) t-butylphenoxy)]aluminum is preferred.

Examples of the tertiary organoaluminum compound represented by the formula (6-2) include diethyl(2,6-di-t-butyl-4-methylphenoxy)aluminum and diethyl(2,6-diethyl). -t-butylphenoxy)aluminum, diisobutyl(2,6-di-t-butyl-4-methylphenoxy)aluminum, diisobutyl(2,6-di-t-butylphenoxy)aluminum, di n-octyl(2,6-di-t-butyl-4-methylphenoxy)aluminum, din-octyl(2,6-di-t-butylphenoxy)aluminum, etc. are mentioned.

The amount of the tertiary organoaluminum compound to be used can be appropriately selected depending on the type of solvent and various polymerization conditions. mol is preferable, 5 mol is more preferable, and 4 mol is still more preferable. On the other hand, as a lower limit of the usage-amount with respect to 1 mol of organolithium compound, 1 mol is preferable, 1.1 mol is more preferable, and 1.2 mol is still more preferable. It is economically advantageous that the said usage-amount is less than the said upper limit. On the other hand, the initiation efficiency of anionic polymerization improves that the said usage-amount is more than the said lower limit.

As said Lewis base, what is selected from the group which consists of an ether and a tertiary polyamine is mentioned, for example. This ether means the compound which has an ether bond in a molecule|numerator. A tertiary polyamine means the compound which has two or more tertiary amine structures in a molecule|numerator. Only 1 type may be used for this Lewis base, and 2 or more types may be used for it.

The ether is preferably a cyclic ether having two or more ether bonds in the molecule or an acyclic ether having one or more ether bonds in the molecule from the viewpoint of polymerization initiation efficiency and stability of polymerization terminal anions.

Examples of the cyclic ether having two or more ether bonds in the molecule include crown ethers such as 12-crown-4, 15-crown-5, and 18-crown-6.

Examples of the acyclic ether having at least one ether bond in the molecule include acyclic monoether, acyclic diether, and acyclic polyether.

Examples of the acyclic monoether include dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, and anisole.

Examples of the acyclic diether include 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-diisopropoxyethane, 1,2-dibutoxyethane, 1,2-diphene. Noxyethane, 1,2-dimethoxypropane, 1,2-diethoxypropane, 1,2-diisopropoxypropane, 1,2-dibutoxypropane, 1,2-diphenoxypropane, 1,3 -dimethoxypropane, 1,3-diethoxypropane, 1,3-diisopropoxypropane, 1,3-dibutoxypropane, 1,3-diphenoxypropane, 1,4-dimethoxybutane, 1, 4-diethoxybutane, 1,4-diisopropoxybutane, 1,4-dibutoxybutane, 1,4-diphenoxybutane, etc. are mentioned.

Examples of the acyclic polyether include diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dibutylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, dibutylene glycol diethyl. Ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tributylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, tributylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetra Propylene glycol dimethyl ether, tetrabutylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetrapropylene glycol diethyl ether, tetrabutylene glycol diethyl ether, etc. are mentioned.

The ether is preferably an acyclic ether having one or two ether bonds in the molecule from the viewpoint of suppression of side reactions and ease of availability, and more preferably diethyl ether or 1,2-dimethoxyethane. Do.

Examples of the tertiary polyamine include N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N',N" chain polyamines such as ,N″-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, and tris[2-(dimethylamino)ethyl]amine; 1,3,5-trimethylhexahydro-1,3,5-triazine, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4,7,10,13,16- non-aromatic heterocyclic compounds such as hexamethyl-1,4,7,10,13,16-hexaazacyclooctadecane; and aromatic heterocyclic compounds such as 2,2'-bipyridyl and 2,2':6',2"-terpyridine.

Moreover, the compound which has one or more ether bonds and one or more tertiary amine structures in a molecule|numerator may be sufficient as a Lewis base. As such a compound, tris[2-(2-methoxyethoxy)ethyl]amine etc. are mentioned, for example.

As an upper limit of the usage-amount of the Lewis base with respect to 1 mol of the said organolithium compound, 5 mol is preferable, 3 mol is more preferable, and 2 mol is more preferable. On the other hand, as a lower limit of the said usage-amount, 0.3 mol is preferable, 0.5 mol is more preferable, and 1 mol is more preferable. It is economically advantageous that the said usage-amount is less than the said upper limit. On the other hand, the initiation efficiency of anionic polymerization improves that the said usage-amount is more than the said lower limit.

Moreover, as an upper limit of the usage-amount of the Lewis base with respect to 1 mol of the said tertiary organoaluminum compound, 1.2 mol is preferable and 1 mol is more preferable. On the other hand, as a lower limit of the said usage-amount, 0.2 mol is preferable and 0.3 mol is more preferable.

1st polymerization process WHEREIN: You may add another additive to a polymerization reaction system as needed. Examples of such other additives include inorganic salts such as lithium chloride; metal alkoxides such as lithium methoxyethoxyethoxide and potassium t-butoxide; Tetraethylammonium chloride, tetraethylphosphonium bromide, etc. are mentioned.

It is preferable to perform anionic polymerization in a 1st polymerization process in presence of an organic solvent from a viewpoint of temperature control being easy, and a viewpoint of uniformizing the inside of a system and advancing anionic polymerization smoothly. Examples of the organic solvent include hydrocarbons such as toluene, xylene, cyclohexane, and methylcyclohexane from the viewpoints of safety, separability from water in washing the reaction mixture after anionic polymerization, and ease of recovery and reuse; Halogenated hydrocarbons, such as chloroform, methylene chloride, and carbon tetrachloride, etc. are preferable. These organic solvents may be used individually by 1 type, and may use 2 or more types together. Moreover, from a viewpoint of advancing anionic polymerization smoothly, it is preferable to deaerate an organic solvent previously in inert gas presence while performing a drying process.

In the first polymerization step, the amount of the organic solvent to be used relative to 100 parts by mass of the monomer (active energy ray-curable monomer and mono(meth)acrylic ester and other monomers as optional components) to be used is the monomer, the organolithium compound, the agent It can be appropriately adjusted depending on the type of tertiary organoaluminum compound, Lewis base, other additives, organic solvent, etc., but from viewpoints of smooth progress of anionic polymerization, separation of the resulting (meth)acrylic polymer (X), waste liquid treatment, etc. In , as an upper limit of the said usage-amount, 10,000 mass parts is preferable and 3,000 mass parts is more preferable. On the other hand, as a lower limit of the said usage-amount, 150 mass parts is preferable and 200 mass parts is more preferable.

As a minimum of the reaction temperature of the anionic polymerization in a 1st polymerization process, -100 degreeC is preferable and -30 degreeC is more preferable. On the other hand, as an upper limit of the reaction temperature of the said anionic polymerization, 50 degreeC is preferable and 25 degreeC is more preferable. When the reaction temperature of the anionic polymerization is equal to or higher than the lower limit, a decrease in the polymerization rate is suppressed and productivity is improved. On the other hand, when the reaction temperature of the anionic polymerization is below the upper limit, polymerization in the active energy ray-curable group in the active energy ray-curable monomer can be more effectively suppressed, and the obtained (meth)acrylic polymer (X) activity Energy-beam sclerosis|hardenability improves.

The anionic polymerization in the first polymerization step is preferably performed in an atmosphere of an inert gas such as nitrogen, argon or helium. Moreover, it is preferable to carry out under sufficient stirring conditions so that the reaction system of anionic polymerization may become uniform.

In the first polymerization process, the monomer (active energy ray-curable monomer and optional mono(meth)acrylic ester and other monomers), the organolithium compound, the tertiary organoaluminum compound and the Lewis base are added to the polymerization reaction system. It is not particularly limited. For example, a tertiary organoaluminum compound may be added to a polymerization reaction system before the monomer to be used, and may be added simultaneously. When adding to a polymerization reaction system simultaneously with the monomer using a tertiary organoaluminum compound, you may add after mixing separately before adding a tertiary organoaluminum compound and the said monomer to a polymerization reaction system. Moreover, it is preferable to add a Lewis base so that it may contact with a tertiary organoaluminum compound before contact with an organolithium compound.

(Second polymerization process)

In a 2nd polymerization process, the monomer which is a monomer which does not contain an active energy ray-curable monomer substantially and contains a (meth)acrylic-type monomer is added after a 1st polymerization process, and it carries out anion polymerization. Thereby, the monomer forming the (meth)acrylic polymer block (B) can also be polymerized in the polymer to be the (meth)acrylic polymer block (A) produced in the first polymerization step. Here, as an example in the case of not containing an active energy ray-curable monomer substantially, the content rate of the active energy ray-curable monomer in the monomer used in a 2nd polymerization process is less than 5 mol%, for example, 3 mol% Less than, less than 1 mol%, less than 0.5 mol%, Furthermore, the case where it is 0 mol%, etc. are mentioned.

As said (meth)acrylic-type monomer which the monomer used in the 2nd polymerization process contains, the thing similar to the (meth)acrylic acid ester illustrated in the said (meth)acrylic-type polymer block (B) is mentioned, for example. Only 1 type may be used for this (meth)acrylic acid ester, and 2 or more types may be used for it.

Moreover, in a 2nd polymerization process, you may further add other monomers other than the said (meth)acrylic acid ester as a (meth)acrylic-type monomer or as a monomer other than that. As this other monomer, the thing similar to the other monomer illustrated in the said (meth)acrylic-type polymer block (B) is mentioned, for example. Only 1 type may be used for this other monomer, and 2 or more types may be used for it.

As an upper limit of the usage-amount of the other monomer with respect to the sum total of the said (meth)acrylic acid ester and another monomer, 10 mol% is preferable and 5 mol% is more preferable. When the amount used is equal to or less than the upper limit, the curing rate of the adhesive and the adhesive strength after curing are improved.

It is preferable to pre-dry the monomer used in the 2nd polymerization process similarly to the monomer used in the said 1st polymerization process.

In the second polymerization step, one or two or more of a tertiary organoaluminum compound, a Lewis base, another additive, and an organic solvent may be added to the polymerization reaction system as in the first polymerization step. As a kind of these components, it can be set as the thing similar to the 1st polymerization process. In addition, the usage-amount of these components can be suitably made into preferable amounts according to the kind of organic solvent, other various polymerization conditions, etc., The method in particular of adding these components to a polymerization reaction system is not restrict|limited.

Various conditions, such as reaction temperature of anionic polymerization in a 2nd polymerization process, can be made into the thing similar to a 1st polymerization process.

Further, in the second polymerization step, from the viewpoint of improving the stability of the polymerization terminal anion, after the first polymerization step, a step of adding a monomethacrylic acid ester to anionic polymerization, and thereafter adding a monoacrylic acid ester to anion It is preferable to provide the process of superposing|polymerizing.

As said monomethacrylic acid ester, the thing similar to the monomethacrylic acid ester illustrated in the said (meth)acrylic-type polymer block (B) can be used. As said monoacrylic acid ester, the thing similar to the monoacrylic acid ester illustrated in the said (meth)acrylic-type polymer block (B) can be used. These monomethacrylic acid esters and monoacrylic acid esters may use only 1 type, respectively, and may use 2 or more types.

(third polymerization process)

In a 3rd polymerization process, the monomer which is a monomer containing an active energy ray-curable monomer and also contains a (meth)acrylic-type monomer is added after a 2nd polymerization process, and it carries out anion polymerization. As a result, a new (meth)acrylic polymer block (A) is formed in the polymer produced in the second polymerization step, and one (meth)acrylic polymer block (A) is formed at both ends of one (meth)acrylic polymer block (B). The triblock copolymers each bonded to each other can be easily and reliably obtained.

As a monomer used in a 3rd polymerization process, the thing similar to the monomer used in a 1st polymerization process is mentioned, The overlapping description is abbreviate|omitted here. In addition, the monomer used in the 3rd polymerization process may be the same as or different from the monomer used in the 1st polymerization process.

In the third polymerization step, one or two or more of a tertiary organoaluminum compound, a Lewis base, another additive, and an organic solvent may be added to the polymerization reaction system. As a kind of these components, it can be set as the thing similar to the said 1st polymerization process. In addition, the usage-amount of these components can be suitably made into preferable amounts according to the kind of organic solvent, other various polymerization conditions, etc., The method in particular of adding these components to a polymerization reaction system is not restrict|limited.

Various conditions, such as reaction temperature of anionic polymerization in a 3rd polymerization process, can be made into the thing similar to a 1st polymerization process.

Anionic polymerization can be stopped by adding a polymerization terminator such as a protic compound to the reaction mixture after the second polymerization step and, in some cases, the third polymerization step. As a protic compound, methanol, the methanol solution of acetic acid, the methanol solution of hydrogen chloride, the aqueous solution of acetic acid, the aqueous solution of hydrogen chloride, etc. are mentioned, for example. The amount of the polymerization terminator to be used is preferably in the range of 1 mol or more and 100 mol or less per 1 mol of the organolithium compound.

A well-known method can be employ|adopted as a method of isolate|separating and acquiring a (meth)acrylic-type polymer (X) from the reaction liquid mixture after the said anionic polymerization was stopped. As a method for separating and obtaining this (meth)acrylic polymer (X), for example, a method of pouring the reaction mixture into the poor solvent of the (meth)acrylic polymer (X) to precipitate the (meth)acrylic polymer (X), reaction The method of distilling off an organic solvent from a liquid mixture to obtain a (meth)acrylic-type polymer (X), etc. are mentioned.

When a metal component derived from an organolithium compound and a tertiary organoaluminum compound remains in the obtained (meth)acrylic polymer (X), deterioration of physical properties such as strength after curing of the adhesive, poor transparency, etc. there is For this reason, it is preferable to remove the metal component derived from an organolithium compound and a tertiary organoaluminum compound after stopping anionic polymerization. As the removal method of the said metal component, the washing process using acidic aqueous solution, the adsorption process using adsorbents, such as an ion exchange resin, celite, activated carbon, etc. are mentioned. As said acidic aqueous solution, hydrochloric acid, sulfuric acid aqueous solution, nitric acid aqueous solution, acetic acid aqueous solution, propionic acid aqueous solution, citric acid aqueous solution etc. are mentioned, for example.

According to the manufacturing method of the (meth)acrylic-type polymer (X) mentioned above, the (meth)acrylic-type polymer (X) with a narrow molecular weight distribution is normally obtained, and the (meth)acrylic-type polymer whose molecular weight distribution (Mw/Mn) is 1.5 or less ( X) can be prepared.

[Compound (Y)]

The compound (Y) is a compound having an active energy ray-curable group, and is a compound other than the (meth)acrylic polymer (X). The active energy ray-curable group of this compound (Y) is combined with the (meth)acrylic polymer (X) to cure, or the compound (Y) is cured alone to form a network structure (mutually) entangled with the (meth)acrylic polymer (X) By forming an interpenetrating polymer network (IPN), etc., the adhesive strength and curing speed of a film containing polyvinyl alcohol and a substrate are excellent, and an adhesive with reduced warpage can be obtained. I think.

As the compound (Y), for example, a styrenic compound, a fatty acid vinyl, a compound having a group represented by the following formula (3), a compound having an oxirane ring, a compound having an oxetane ring, vinyl ether, N-vinyl compound, etc. can be heard A compound (Y) may be used individually by 1 type, and may use 2 or more types together. In addition, when the polyfunctional compound (Y) is used as at least a part of the compound (Y), it can act as a crosslinking agent and is preferable.

[Formula 8]

In the formula (3), R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, X ² represents an oxygen atom, a sulfur atom or -NR ⁶ -, wherein R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. represents the flag.

R ⁵ is, for example, a hydrogen atom, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 2-methylbutyl group, 3- Methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group, neopentyl group, n-hexyl group, 2-methylphen Alkyl groups, such as a tyl group, 3-methylpentyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, and n-eicosyl group; Cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group; Aryl groups, such as a phenyl group and a naphthyl group, etc. are mentioned. When R< ⁵ > is a hydrocarbon group, as an upper limit of carbon number, 10 is preferable and 4 is more preferable.

Moreover, the C1-C20 hydrocarbon group represented by R< ⁵ > may have a substituent. As this substituent, what is necessary is just to not impair the active energy ray sclerosis|hardenability of an active energy ray-curable group, For example, Alkoxy groups, such as a methoxy group, an ethoxy group, an isopropoxy group, and t-butoxy group; Halogen atoms, such as a chlorine atom and a bromine atom, etc. are mentioned.

R ⁵ is particularly preferably a hydrogen atom or a methyl group from the viewpoint of being excellent in the availability and curing rate of the compound (Y).

Examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ⁶ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 2- Methylbutyl group, 3-methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group, neopentyl group, n-hexyl group Alkyl groups, such as a real group, 2-methylpentyl group, and 3-methylpentyl group; Cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; Aryl groups, such as a phenyl group, etc. are mentioned.

Moreover, the C1-C6 hydrocarbon group represented by R< ⁶ > may have a substituent. As this substituent, what is necessary is just what does not impair the active energy ray sclerosis|hardenability of an active energy ray-curable group, For example, Alkoxy groups, such as a methoxy group, an ethoxy group, an isopropoxy group, t-butoxy group; Halogen atoms, such as a chlorine atom and a bromine atom, etc. are mentioned.

R ⁶ is preferably a methyl group or an ethyl group from the viewpoint of being excellent in the availability or curing rate of the compound (Y).

An oxygen atom or -NR ⁶ - is preferable, and, as for X ² , an oxygen atom or an oxygen atom is more preferable from the viewpoint of being excellent in the availability and curing rate of the compound (Y).

Examples of the styrene-based compound include styrene, indene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert-butoxystyrene, p-chloromethylstyrene, p-acetoxystyrene, Divinylbenzene etc. are mentioned.

Examples of the fatty acid vinyl include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, and vinyl cinnamate.

Examples of the compound having a group represented by the formula (3) include (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate isopropyl, (meth) acrylate n-butyl , (meth) acrylate isobutyl, (meth) acrylate t-butyl, (meth) acrylate pentyl, (meth) acrylate isoamyl, (meth) acrylic acid hexyl, (meth) acrylate heptyl, (meth) acrylate octyl, (meth) acrylate ) acrylate isooctyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylate nonyl, (meth) acrylate decyl, (meth) acrylate isodecyl, (meth) acrylate undecyl, (meth) acrylate dodecyl, (meth) Lauryl acrylate, (meth) stearyl acrylate, (meth) acrylate isostearyl, (meth) acrylate benzyl, (meth) acrylate isobornyl, (meth) acrylate bornyl, (meth) acrylic acid tricyclodecanyl, ( (meth)acrylic acid dicyclopentanyl, (meth)acrylic acid dicyclopentenyloxyethyl, (meth)acrylic acid 4-butylcyclohexyl, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid ) Acrylic acid 2-hydroxybutyl, (meth)acrylic acid 4-hydroxybutyl, (meth)acrylic acid 2-hydroxy-3-phenoxypropyl, (meth)acrylate butoxyethyl, (meth)acrylic acid ethoxydiethylene glycol , (meth) acrylic acid benzyl, (meth) acrylate phenoxyethyl, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid polyethylene glycol monoester, (meth) acrylic acid polypropylene glycol monoester, (meth) acrylic acid methoxyethylene Glycol, (meth)acrylic acid ethoxyethyl, (meth)acrylic acid methoxypolyethylene glycol, (meth)acrylic acid methoxypolypropylene glycol, (meth)acrylic acid dimethylaminoethyl, (meth)acrylic acid diethylaminoethyl, (meth)acrylic acid 7-amino-3,7-dimethyloctyl, 4-acryloylmorpholine, trimethylolpropane tri(meth)acrylate, trimethylolpropane trioxyethyl(meth)acrylate, pentaerythritol tri(meth)acrylate , Ethylene glycol di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol Both terminals of di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and bisphenol A diglycidyl ether (meth)acrylic acid adduct, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri ( Meth) acrylate, tris (2- (2,3-dihydroxypropoxy) ethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acryl rate, cyclohexanedimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, di(meth)acrylate of diol which is an adduct of ethylene oxide or propylene oxide of bisphenol A, hydrogenated bisphenol A Di(meth)acrylate of diol which is an adduct of ethylene oxide or propylene oxide, epoxy (meth)acrylate obtained by adding (meth)acrylate to diglycidyl ether of bisphenol A, (3-ethyloxetane-3- 1) (meth)acrylate, etc. are mentioned.

Moreover, as another example of the compound which has a group represented by said Formula (3), For example, bisphenol A-type epoxy acrylate resin, phenol novolak-type epoxy acrylate resin, cresol novolak-type epoxy acrylate resin, Epoxy (meth), such as acrylate-based resin; carboxyl group-modified epoxy (meth)acrylate-based resin; Urethane (meth)acrylate-type resin obtained by making the urethane resin obtained from a polyol and organic isocyanate react with hydroxyl-containing (meth)acrylic acid ester; Resin which introduce|transduced the (meth)acryloyl group through the ester bond into the polyol; polyester (meth)acrylate-based resin; (meth)acrylamide type compounds, such as N-hydroxyethyl (meth)acrylamide, etc. are mentioned.

Examples of the polyol include polytetramethylene glycol, polyesterdiol of ethylene glycol and adipic acid, ε-caprolactone-modified polyesterdiol, polypropylene glycol, polyethylene glycol, polycarbonate diol, and hydroxyl-terminated hydrogenated polyisoprene. , hydroxyl terminal polybutadiene, hydroxyl terminal polyisobutylene, and the like.

As said organic isocyanate, tolylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate etc. are mentioned, for example.

As said hydroxyl-containing (meth)acrylic acid ester, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, etc. are mentioned, for example. can

Examples of the compound having an oxirane ring include dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, Bis(3,4-epoxycyclohexylmethyl)adipate, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, polytetramethylene glycol diglycidyl Dilether, hydrogenated bisphenol A diglycidyl ether, epoxidized vegetable oil, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, polybutadiene diglycidyl ether having both hydroxyl groups, internal epoxidation of polybutadiene, double bond of styrene-butadiene copolymer This partially epoxidized compound (“Epofriend” from Daicel Chemical Industry Co., Ltd., etc.), a compound in which the isoprene unit of a block copolymer of ethylene-butylene copolymer and polyisoprene is partially epoxidized (“L-207” by KRATON Corporation) etc.), polyamideamine epichlorhydrin, etc. are mentioned.

Examples of the compound having an oxetane ring include alkoxyalkyl group-containing monofunctional oxetane such as 3-ethyl-3-hydroxymethyloxetane and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane. Monofunctional oxetane containing aromatic groups, such as 3-ethyl-3-phenoxymethyloxetane, xylylenebisoxetane, 1,4-bis[(3-ethyloxetan-3-yl)methoxymethyl]benzene , 1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, 1,2-bis [(3-ethyloxetan-3-yl)methoxy]benzene, 4,4'-bis[(3-ethyloxetan-3-yl)methoxy]biphenyl, 2,2'-bis[(3 -Ethyloxetan-3-yl)methoxy]biphenyl, 3,3',5,5'-tetramethyl-4,4'-bis[(3-ethyloxetan-3-yl)methoxy]bi Phenyl, 2,7-bis[(3-ethyloxetan-3-yl)methoxy]naphthalene, bis[4-{(3-ethyloxetan-3-yl)methoxy}phenyl]methane, bis[2 -{(3-ethyloxetan-3-yl)methoxy}phenyl]methane, 2,2-bis[4-{(3-ethyloxetan-3-yl)methoxy}phenyl]propane, novolak type Etherification modified product of phenol-formaldehyde resin with 3-chloromethyl-3-ethyloxetane, 3(4),8(9)-bis[(3-ethyloxetan-3-yl)methoxymethyl] -tricyclo[5.2.1.0 ^2,6 ]decane, 2,3-bis[(3-ethyloxetan-3-yl)methoxymethyl]norbornane, 1,1,1-tris[(3-ethyl Oxetan-3-yl)methoxymethyl]propane, 1-butoxy-2,2-bis[(3-ethyloxetan-3-yl)methoxymethyl]butane, 1,2-bis[{2- (3-ethyloxetan-3-yl)methoxy}ethylthio]ethane, bis[{4-(3-ethyloxetan-3-yl)methylthio}phenyl]sulfide, 1,6-bis[( 3-ethyloxetan-3-yl)methoxy]-2,2,3,3,4,4,5,5-octafluorohexane, 3-[(3-ethyloxetan-3-yl)me Toxy]propyltrimethoxysilane, 3-[(3-ethyloxetan-3-yl)methoxy]propyltriethoxysilane, 3-[(3-ethyloxetan-3-yl)methoxy]propyltri The hydrolysis-condensation product of an alkoxysilane, the condensate of tetrakis[(3-ethyloxetan-3-yl)methyl]silicate, etc. are mentioned.

Examples of the vinyl ether include cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol divinyl ether, cyclohexane. Dimethanol divinyl ether, etc. are mentioned.

As said N-vinyl compound, N-vinylpyrrolidone, N-vinylmorpholine, etc. are mentioned, for example.

The compound (Y) is selected from the group consisting of a compound having a group represented by the formula (3), a compound having an oxirane ring, and a compound having an oxetane ring from the viewpoints of handling, reactivity and adhesiveness among these. At least one is preferable, (meth)acrylic acid tetrahydrofurfuryl, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, tris(2-hydroxyethyl)isocyanurate tri (meth)acrylate is more preferable. When a radical-reactive compound such as a compound having a group represented by the formula (3) is used as the compound (Y), the adhesive to be obtained or the cured product after curing it tends to have improved adhesion to the substrate. In addition, when a cation-reactive compound such as a compound having an oxirane ring or a compound having an oxetane ring is used as the compound (Y), the adhesive obtained and the cured product after curing the adhesive and the polyvinyl alcohol-containing film tends to improve. From the viewpoint of improving the adhesion to both the substrate and the film containing polyvinyl alcohol, it is preferable to use both a radically reactive compound and a cationically reactive compound as the compound (Y), and in particular, a group represented by the above formula (3) It is more preferable to use together the compound which has a compound and the compound which has an oxirane ring, and/or the compound which has an oxetane ring.

In addition, from the viewpoint of bonding the active energy ray-curable group of the (meth)acrylic polymer (X) to the compound (Y), when the active energy ray-curable group of the (meth)acrylic polymer (X) is a radical reactive group, the compound ( At least a part of Y) is preferably a radical-reactive compound, and when the active energy ray-curable group of the (meth)acrylic polymer (X) is a cation-reactive group, at least a part of the compound (Y) is a cation-reactive compound It is preferable to be Specifically, when the active energy ray-curable group of the (meth)acrylic polymer (X) is a group having a group represented by the formula (1), at least a part of the compound (Y) is a compound having a group represented by the formula (3) Preferably, when the active energy ray-curable group of the (meth)acrylic polymer (X) is a group having an oxirane ring and/or a group having an oxetane ring, at least a part of the compound (Y) is a compound having an oxirane ring, and It is preferable that it is a compound which has/or an oxetane ring.

As a lower limit of the content rate of the compound (Y) in the said adhesive agent (1), 10 mass % is preferable, 30 mass % is more preferable, 50 mass % is still more preferable. On the other hand, as an upper limit of the said content rate, 99 mass % is preferable, 95 mass % is more preferable, and 90 mass % is still more preferable, and the said content rate is 85 mass % or less, 80 mass % or less, Furthermore, 75 mass % or less. % or less. When the said content is more than the said minimum, the viscosity of the said adhesive agent can be maintained moderately, and handleability improves. On the other hand, when the said content is below the said upper limit, mechanical properties, such as adhesive strength of the said adhesive agent, improve more.

[Active energy ray polymerization initiator (P)]

The adhesive (1) preferably further contains an active energy ray polymerization initiator (P) in addition to the (meth)acrylic polymer (X) and the compound (Y). An active energy ray polymerization initiator (P) can accelerate|stimulate reaction of the (meth)acrylic-type polymer (X) and compound (Y) which the said adhesive agent contains by irradiating an active energy ray. As such an active energy ray polymerization initiator (P), for example, the compound which generate|occur|produces a radical by irradiating an active energy ray (radical polymerization initiator (R)), the compound which generate|occur|produces a cation (cationic polymerization initiator (C)) and a compound that generates a base, and may be appropriately selected according to the type of the (meth)acrylic polymer (X) or compound (Y) used.

As said radical polymerization initiator (R), For example, Carbonyl compounds, such as acetophenones, benzophenones, Michler ketones, and benzoin; Sulfur compounds, such as tetramethylthiuram monosulfide and thioxanthone, etc. are mentioned. These radical polymerization initiators (R) may be used individually by 1 type, and may use 2 or more types together.

Examples of the acetophenones include 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, and 2-hydroxy-2-methyl-1-phenyl. propan-1-one and the like.

Examples of the benzophenones include benzophenone, benzoylbenzoic acid, hydroxybenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, and acrylated benzophenone.

As said benzoins, benzoin, benzoin methyl ether, benzoin isopropyl ether, etc. are mentioned, for example.

As a radical polymerization initiator (R), acetophenones or benzophenones are preferable from points, such as reactivity and transparency, among these, and 1-hydroxycyclohexylphenyl ketone is more preferable.

As a commercial item of the said radical polymerization initiator (R), "IRGACURE 184" (1-hydroxycyclohexylphenyl ketone; BASF make), "Solvathlon BIPE" (made by Kurogane Chemicals), "Solvathlon BIBE", for example, (manufactured by Kurogane Chemical Co., Ltd.), "IRGACURE 651" (2,2-dimethoxy-1,2-diphenylethan-1-one; manufactured by BASF), "DAROCUR 1173" (2-hydroxy-2-methyl-1 -Phenylpropan-1-one; manufactured by BASF), "IRGACURE 2959" (manufactured by BASF), "IRGACURE 127" (manufactured by BASF), "IRGACURE 907" (manufactured by BASF), "IRGACURE 369" (manufactured by BASF), "KAYACURE" BP" (manufactured by Nippon Kayakus), "IRGACURE 379" (manufactured by BASF), "DAROCUR TPO" (manufactured by BASF), "IRGACURE 819" (manufactured by BASF), "IRGACURE 819DW" (manufactured by BASF), "IRGACURE 784" (manufactured by BASF) manufacture), "IRGACURE OXE 01" (manufactured by BASF), "IRGACURE OXE 02" (manufactured by BASF), "IRGACURE 754" (manufactured by BASF), "IRGACURE 500" (manufactured by BASF), "IRGACURE 1800" (manufactured by BASF), "IRGACURE 1870" (manufactured by BASF), "DAROCUR 4265" (manufactured by BASF), "KAYACURE DETX-S" (manufactured by Nippon Kayaku Co., Ltd.), "ESACURE KIP 150" (manufactured by Lamberti), "S-121" (manufactured by Shinko Kiken) , "Seikuol BEE" (manufactured by Seco Chemical), and the like.

Examples of the cationic polymerization initiator (C) include onium salt-based initiators such as sulfonium salt-based initiators and iodonium salt-based initiators, sulfonic acid derivatives, carboxylate esters, aryldiazonium salts, iron arene complexes, pyridinium salts, A quinolinium salt, an O-nitrobenzyl group containing compound, etc. are mentioned. These cationic polymerization initiators (C) may be used individually by 1 type, and may use 2 or more types together.

Examples of the sulfonium salt-based initiator include p-hydroxyphenylbenzylmethyl such as p-phenylbenzylmethylsulfonium salt, p-phenyldimethylsulfonium salt, and benzylmethyl p-hydroxyphenylsulfonium hexafluoroantimonate. Triarylsulfonium salts such as sulfonium salt, triphenylsulfonium salt, diphenyl-4-(phenylthio)phenylsulfonium salt, and diphenyl-4-thiophenoxyphenylsulfonium salt, 4,4-bis[di(β-) and disulfonium salts having a bis[4-(diphenylsulfonio)phenyl]sulfide skeleton such as hydroxyethoxy)phenylsulfonio]phenylsulfidebishexafluoroantimonate.

Examples of the counter anions of these sulfonium salts include SbF ₆ ^- , AsF ₆ ^- , PF ₆ ^- , BF ₄ ^- and the like, and among these, PF ₆ ^- and SbF ₆ ^- are preferable from the viewpoint of reactivity and stability.

Examples of the iodonium salt-based initiator include diphenyliodonium, bis(4-tert-butylphenyl)iodonium, (4-tert-butoxyphenyl)phenyliodonium, and (4-methoxyphenyl)phenyliodonium. iodonium salts, such as nium, etc. are mentioned.

As the cationic polymerization initiator (C), triarylsulfonium salts such as diphenyl-4-(phenylthio)phenylsulfonium salt and diphenyl-4-thiophenoxyphenylsulfonium salt are preferable from the viewpoint of thermal stability. Do.

As a commercial item of the said cationic polymerization initiator (C), "CPI-100P" (made by San Apro), "CPI-101A" (made by San Apro), "IRGACURE 250" (made by BASF), "Adeca", for example "Optomer SP-172" (manufactured by ADEKA), "Adeka Optomer SP-170" (manufactured by ADEKA), "Adeka Optomer SP-152" (manufactured by ADEKA), "Adeka Optomer SP-150" (made by ADEKA) Manufactured), "San-Aid SI-60L" (manufactured by Sanshin Chemical Industry), "San-Aid SI-80L" (manufactured by Sanshin Chemical Industry), "San-Aid SI-100L" (manufactured by Sanshin Chemical Industry), "San-Aid SI-" 150L" (manufactured by Sanshin Chemical Industry Co., Ltd.); and the like.

The lower limit of the amount of the active energy ray polymerization initiator (P) with respect to 100 parts by mass of the (meth)acrylic polymer (X) in the adhesive (1) is preferably 0.01 parts by mass, more preferably 0.05 parts by mass, and 0.1 A mass part is more preferable, 1 mass part, 3 mass parts, Furthermore, 5 mass parts may be sufficient. On the other hand, as an upper limit of the said amount, 50 mass parts is preferable, 40 mass parts is more preferable, 20 mass parts, 10 mass parts, Furthermore, 8 mass parts may be sufficient. When the amount is equal to or greater than the lower limit, the curing rate of the adhesive and the adhesive strength after curing are improved. On the other hand, when the said amount is below the said upper limit, reduction in molecular weight of the hardened|cured material by the hardening rate becoming fast too much is suppressed, and heat resistance improves.

[Other Optional Ingredients]

The said adhesive agent (1) may contain other components other than a (meth)acrylic-type polymer (X), a compound (Y), and an active energy ray polymerization initiator (P) further. As said other component, a crosslinking agent, a sensitizer, a diluent, a tackifier, a softener, a filler, a stabilizer, a pigment, dye etc. are mentioned, for example. The said other component may be an organic compound or an inorganic compound may be sufficient as it.

(crosslinking agent)

The crosslinking agent crosslinks the (meth)acrylic polymer (X), the compound (Y), and the like, thereby improving the strength after curing of the adhesive and the adhesive strength between the film and the base material including polyvinyl alcohol. Moreover, only 1 type may be used for the said crosslinking agent, and may use 2 or more types together.

Examples of the crosslinking agent include nitrogen compounds such as polyoxazoline, isocyanate compounds such as diphenylmethane diisocyanate, aldehyde compounds such as glutaraldehyde, zirconium compounds such as zirconium ammonium carbonate, titanium compounds such as titanium lactate, etc. can be heard

As an upper limit of the content rate of the crosslinking agent in the said adhesive agent, 20 mass % is preferable and 15 mass % is more preferable. On the other hand, as a lower limit of the said content rate, 1 mass % is preferable and 3 mass % is more preferable. When the said content is below the said upper limit, the viscosity of the said adhesive agent can be maintained moderately and handleability improves.

(sensitizer)

The said sensitizer accelerates hardening of the said adhesive agent by moving or broadening the sensitivity of an active energy ray. Examples of such a sensitizer include n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiouric acid and triethylamine, and triethylamine is preferred.

It is preferable to use the said sensitizer together with an active energy ray polymerization initiator (P). When using a sensitizer and an active energy ray polymerization initiator (P) together, 10 % is preferable as the minimum of the mass ratio of the sensitizer with respect to the sum total of an active energy ray polymerization initiator (P) and a sensitizer, and 20 % is more preferable. On the other hand, as an upper limit of the said mass ratio, 90 % is preferable and 80 % is more preferable.

(diluent)

The said diluent adjusts the viscosity of the said adhesive agent by adding to the said adhesive agent, and the mechanical strength after hardening of the said adhesive agent. Examples of the diluent include compounds not having an active energy ray-curable group, and specifically, for example, phthalic acid esters, non-aromatic dibasic acid esters, aliphatic esters, polyalkylene glycol esters, phosphoric acid esters, trimelli and tonic acid esters, chlorinated paraffins, hydrocarbon oils, process oils, polyethers, polyester plasticizers obtained from dibasic acids and dihydric alcohols, and vinyl polymers obtained by polymerizing vinyl monomers. . These inactive compounds may be used individually by 1 type, and may use 2 or more types together. Moreover, a diluent may have functional groups (a hydroxyl group, a carboxyl group, a halogen group, etc.) other than an active energy ray-curable group.

As said phthalic acid ester, dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, butylbenzyl phthalate, etc. are mentioned, for example.

As said non-aromatic dibasic acid ester, dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, etc. are mentioned, for example.

As said aliphatic ester, butyl oleate, methyl acetylricinoleate, etc. are mentioned, for example.

As ester of the said polyalkylene glycol, diethylene glycol dibenzoate, triethylene glycol dibenzoate, pentaerythritol ester, etc. are mentioned, for example.

As said phosphoric acid ester, tricresyl phosphate, tributyl phosphate, etc. are mentioned, for example.

Examples of the hydrocarbon-based flow path include alkyldiphenyl and partially hydrogenated terphenyl.

As said polyether, For example, polyether polyol; and derivatives obtained by converting the hydroxyl group of the polyether polyol into an ester group, an ether group, or the like. Here, as a polyether polyol, polyethyleneglycol, polypropylene glycol, polytetramethylene glycol, etc. are mentioned, for example.

As said dibasic acid, sebacic acid, adipic acid, azelaic acid, phthalic acid etc. are mentioned, for example. As said dihydric alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol etc. are mentioned, for example.

Examples of the vinyl polymer include (meth)acrylic polymer, polybutene, polyisobutylene, styrenic polymer (polystyrene, poly-α-methylstyrene, etc.), diene polymer (polybutadiene, polychloroprene, etc.) , vinyl ether polymers, copolymers thereof (butadiene-acrylonitrile copolymer, etc.), and the like.

As the diluent, a polymer having a number average molecular weight (Mn) of 400 or more and 15,000 or less is preferable. As a minimum of Mn of the said polymer, 800 is more preferable, and 1,000 is more preferable. On the other hand, as an upper limit of Mn of the said polymer, 10,000 is more preferable, and 8,000 is more preferable. When the Mn is equal to or greater than the lower limit, it is possible to suppress the time-lapse of outflow of the diluent from the cured product after curing the adhesive, so that the initial physical properties can be maintained for a long period of time. Moreover, when the said Mn is below the said upper limit, the handleability of the said adhesive agent improves.

When the diluent is a polymer, the molecular weight distribution (Mw/Mn) is not particularly limited, but is usually less than 1.8, preferably 1.7 or less, more preferably 1.6 or less, still more preferably 1.5 or less, and more preferably 1.4 or less. It is particularly preferred, and 1.3 or less is most preferred.

The diluent is preferably compatible with the (meth)acrylic polymer (X), and when the diluent is a polymer, a vinyl polymer is more preferable in terms of compatibility, weather resistance and heat resistance, and a (meth)acrylic polymer is more preferable. , acrylic polymers are particularly preferred.

Examples of the acrylic polymer include n-butyl polyacrylate and 2-ethylhexyl polyacrylate. As a synthesis method of this acrylic polymer, a solution polymerization method, a high temperature continuous polymerization method, a living radical polymerization method, etc. are mentioned, for example.

As a method for synthesizing the acrylic polymer, a high-temperature continuous polymerization method is preferable from the viewpoint of synthesizing the acrylic polymer without using a solvent or a chain transfer agent. As this high-temperature continuous polymerization method, the method etc. described in USP4414370, Unexamined-Japanese-Patent No. 59-6207, Unexamined-Japanese-Patent No. 5-58005, Unexamined-Japanese-Patent No. 1-313522, USP5010166 etc. are mentioned, for example. can Examples of the acrylic polymer synthesized by such a high-temperature continuous polymerization method include Dong-A Synthetic Products UP series (refer to the October 1999 issue of Industrial Materials) and the like.

Moreover, as a method of synthesizing the acrylic polymer, a living radical polymerization method is preferable, and an atom transfer radical polymerization method is more preferable from the viewpoint that a polymer having a narrow molecular weight distribution can be obtained and the viscosity of the adhesive can be reduced.

As a minimum of the usage-amount of the diluent with respect to 100 mass parts of (meth)acrylic-type polymer (X), 5 mass parts is preferable, 10 mass parts is more preferable, and 20 mass parts is still more preferable. On the other hand, as an upper limit of the said usage-amount, 150 mass parts is preferable, 120 mass parts is more preferable, and 100 mass parts is more preferable. When the said usage-amount is more than the said lower limit, the viscosity of the said adhesive agent, and the mechanical strength after hardening the said adhesive agent can be adjusted more effectively. On the other hand, when the said usage-amount is below the said upper limit, the mechanical strength of hardened|cured material improves.

(tackifier)

The said tackifier provides adhesiveness to the hardened|cured material after hardening the said adhesive agent. Examples of the tackifier include chroman indene resin, phenol resin, pt-butylphenol acetylene resin, phenol formaldehyde resin, terpene resin, synthetic terpene resin, aromatic modified terpene resin, xylene formaldehyde resin, Aromatic hydrocarbon resins, alicyclic hydrocarbon resins, monoolefin or diolefin oligomers, hydrocarbon resins, hydrogenated hydrocarbon resins, polybutenes, polyhydric alcohol esters of rosin, hydrogenated rosin, hydrogenated wood rosin, hydrogenated rosin and mono Ester of alcohol or polyhydric alcohol, terepine resin, etc. are mentioned. Among these, terpene resins, synthetic terpene resins, aromatic modified terpene resins, aliphatic saturated petroleum resins, rosin esters, disproportionated rosin esters, hydrogenated rosin esters, aliphatic petroleum resins (C5 aliphatic petroleum resins, C5·C9 series) aliphatic petroleum resin, etc.), or a modified aliphatic petroleum resin is preferred.

[Method for Producing Adhesive (1)]

The adhesive (1) can be conveniently produced by mixing and stirring the (meth)acrylic polymer (X), the compound (Y), and other optional components (active energy ray polymerization initiator (P) or other optional components).

<Adhesive (2)>

The adhesive (2) is an adhesive for adhering a film containing polyvinyl alcohol to a substrate, and a polymer (X') having an active energy ray-curable group, and a compound having an active energy ray-curable group other than the polymer (X') (Y') is contained, and the crosslinking density calculated|required from the storage elastic modulus of the rubber-like flat area|region obtained by dynamic viscoelasticity measurement after hardening is 0.4 mol/L or more and 2 mol/L or less.

The adhesive (2) has an excellent balance between the adhesive strength to the film and substrate containing polyvinyl alcohol and the strength of the cured product itself because the crosslinking density after curing is in a specific range, so the adhesive strength is excellent. It is thought that the adhesive body with improved curvature and reduced warpage can be obtained, and the curing rate is also excellent.

The lower limit of the crosslinking density is preferably 0.5 mol/L, more preferably 1 mol/L, still more preferably 1.3 mol/L, particularly preferably 1.4 mol/L, and most preferably 1.5 mol/L. Do. Moreover, as an upper limit of the said crosslinking density, 1.9 mol/L is preferable, 1.8 mol/L is more preferable, 1.7 mol/L is still more preferable, and 1.6 mol/L is especially preferable. When the crosslinking density is at least the lower limit, the strength of the cured product itself after curing the adhesive is improved. On the other hand, when the crosslinking density is below the upper limit, the deformation followability of the obtained cured product is improved. The adhesiveness to the film and base material containing alcohol is improved, and the curvature of an adhesive agent is further reduced. The crosslinking density is, for example, by increasing the content rate of the active energy ray-curable group in the polymer (X') or by increasing the content rate of the polyfunctional compound in the compound (Y'). value can be increased.

The said crosslinking density measures dynamic viscoelasticity with respect to the hardened|cured material after hardening an adhesive agent, and calculates|requires it from the storage elastic modulus of the rubber-like flat area|region obtained by it. That is, the storage elastic modulus (E': unit is Pa) and the obtained crosslinking density (ν: unit is mol/m3) are, E' = 3νRT (where R represents a gas constant, T is absolute temperature (unit is K) It can be considered that the relationship of ) is satisfied, and can be calculated from the relationship. The storage elastic modulus of hardened|cured material, for example, apply|coats an adhesive agent on the base film which carried out the release process, irradiates an ultraviolet-ray so that it may become 700 mJ/cm<2>, Then, after leaving still at the temperature of 23 degreeC and 50% of relative humidity for 24 hours, the base film About the sample of the hardened|cured material obtained by peeling from from, it can measure using a dynamic viscoelasticity measuring apparatus, and can measure by the method specifically described in an Example. In addition, the rubbery flat region can be obtained from a graph showing the relationship between the measurement temperature and the storage modulus, and in particular, when the glass transition point (Tg) of the cured product is sufficiently smaller than 120°C, the crosslinking density is the storage modulus of 150°C. It can be obtained from the above formula using the value of .

The adhesive (2) has a storage elastic modulus at 150° C. of 4 × 10 ⁶ Pa or more and 21 × 10 ⁶ Pa or less obtained by the dynamic viscoelasticity measurement described above. It is preferable from a viewpoint of reduction of the curvature of an adhesive agent, etc. The lower limit of the storage elastic modulus at 150°C is preferably 6 × 10 ⁶ Pa, more preferably 10 × 10 ⁶ Pa, still more preferably 14 × 10 ⁶ Pa, particularly preferably 15 × 10 ⁶ Pa, 16 × 10 ⁶ Pa is most preferred. Moreover, as an upper limit of the said 150 degreeC storage elastic modulus, 20 x 10 ⁶ Pa is preferable, 19 x 10 ⁶ Pa is more preferable, 18 x 10 ⁶ Pa is still more preferable, 17 x 10 ⁶ Pa is more preferable. Do. When the said 150 degreeC storage elastic modulus is more than the said minimum, the intensity|strength of the hardened|cured material itself after hardening the said adhesive agent improves. On the other hand, when the crosslinking density is equal to or less than the upper limit, the adhesiveness to the film and the base material containing polyvinyl alcohol is improved, and the warpage of the adhesive is further reduced due to the fact that the deformation followability of the obtained cured product is improved. . In addition, the said 150 degreeC storage modulus makes the content rate of the active energy ray-curable group in a polymer (X') high, or the content rate of the polyfunctional compound in a compound (Y'), for example, or By doing so, the value can be made high.

The polymer (X') is not particularly limited in its kind as long as it has an active energy ray-curable group, and a preferable example thereof is the above-described (meth)acrylic polymer (X) in the adhesive (1) (eg, terminal and / or a (meth)acrylic polymer having a (meth)acryloyloxy group in the side chain (acrylic resin (meth)acrylate, etc.), as a more preferable example, a (meth)acrylic polymer block (A) having an active energy ray-curable group and block copolymers having a (meth)acrylic polymer block (B) that does not substantially have an active energy ray-curable group, etc.).

As another preferable example of polymer (X'), urethane (meth)acrylate is mentioned. There is no restriction|limiting in particular in the kind of the said urethane (meth)acrylate, Polyester type, polyether type, urethane (meth)acrylate, such as a polycarbonate type, can be used. Common urethane (meth)acrylates usually have a (meth)acryloyl group at the terminal of the polymer chain and have a relatively low content of active energy ray-curable groups. It is preferable to make the content rate of a functional compound high. Description of the active energy ray-curable group which the polymer (X') has is the same as the description of the active energy ray-curable group which the (meth)acrylic-type polymer (X) has in the adhesive agent (1).

Although there is no particular limitation on the number average molecular weight (Mn) of the polymer (X'), from the viewpoints of handling, fluidity, and mechanical properties of the polymer (X'), the lower limit of Mn is preferably 1,000, and 2,000 is More preferably, 2,500 is more preferable, 4,000 is particularly preferable, and 5,000 is most preferable, and the polymer (X') having a number average molecular weight (Mn) of 7,000 or more may be preferably used. On the other hand, the upper limit of Mn is preferably 7,000,000, more preferably 3,000,000, and still more preferably 2,000,000 from the viewpoint of suppressing the increase in viscosity of the obtained adhesive or the preparation thereof.

As a lower limit of the content rate of the polymer (X') in the said adhesive agent (2), 1 mass % is preferable, 3 mass % is more preferable, 5 mass % is still more preferable, 10 mass % is especially preferable, , the content may be 15% by mass or more. On the other hand, as an upper limit of the said content rate, 90 mass % is preferable, 70 mass % is more preferable, and 50 mass % is especially preferable. When the said content is more than the said lower limit, mechanical properties, such as adhesive strength of the said adhesive agent, improve more, and the adhesive body with which curvature was further reduced can be obtained. On the other hand, when the said content rate is below the said upper limit, the viscosity of the said adhesive agent can be maintained moderately, and handleability improves.

The compound (Y') is a compound having an active energy ray-curable group other than the polymer (X'), and among the compounds (Y) described above in the adhesive (1), those which do not correspond to the polymer (X') are mentioned . The molecular weight of the compound (Y') is not particularly limited, but from the viewpoints of improving adhesion to a film and a substrate containing polyvinyl alcohol and reducing warpage of the obtained adhesive, the molecular weight is preferably less than 4,000, less than 2,000 This is more preferable, and less than 1,000 is more preferable.

From the viewpoint of bonding the active energy ray-curable group of the polymer (X') to the compound (Y'), when the active energy ray-curable group of the polymer (X') is a radically reactive group, at least a part of the compound (Y') is It is preferable that it is a radical-reactive compound, and when the active energy ray-curable group which the polymer (X') has is a cation-reactive group, it is preferable that at least one part of compound (Y') is a cation-reactive compound. Specifically, when the active energy ray-curable group of the polymer (X') is a group having a group represented by the formula (1), at least a part of the compound (Y') is preferably a compound having a group represented by the formula (3), , when the active energy ray-curable group of the polymer (X') is a group having an oxirane ring and/or a group having an oxetane ring, at least a part of the compound (Y') is a compound having an oxirane ring and/or oxetane It is preferable that it is a compound which has a ring.

As a lower limit of the content rate of the compound (Y') in the said adhesive agent (2), 10 mass % is preferable, 30 mass % is more preferable, 50 mass % is still more preferable. On the other hand, as an upper limit of the said content rate, 99 mass % is preferable, 95 mass % is more preferable, and 90 mass % is still more preferable, and the said content rate is 85 mass % or less, 80 mass % or less, Furthermore, 75 mass % or less. % or less. When the said content is more than the said minimum, the viscosity of the said adhesive agent can be maintained moderately, and handleability improves. On the other hand, when the said content is below the said upper limit, mechanical properties, such as adhesive strength of the said adhesive agent, improve more.

Also in the adhesive agent (2), similarly to the adhesive agent (1), it is preferable to further contain an active energy ray polymerization initiator (P) other than a polymer (X') and a compound (Y'). Description of the active energy ray polymerization initiator (P) in the adhesive agent (2) is the same as description of the active energy ray polymerization initiator (P) in the adhesive agent (1).

The lower limit of the amount of the active energy ray polymerization initiator (P) with respect to 100 parts by mass of the polymer (X') in the adhesive (2) is preferably 0.01 parts by mass, more preferably 0.05 parts by mass, and still more preferably 0.1 parts by mass. and 1 part by mass, 3 parts by mass, or 5 parts by mass may be applied. On the other hand, as an upper limit of the said amount, 50 mass parts is preferable, 40 mass parts is more preferable, 20 mass parts, 10 mass parts, Furthermore, 8 mass parts may be sufficient. When the amount is equal to or greater than the lower limit, the curing rate of the adhesive and the adhesive strength after curing are improved. On the other hand, when the said amount is below the said upper limit, reduction in molecular weight of the hardened|cured material by the hardening rate becoming fast too much is suppressed, and heat resistance improves.

Also in the adhesive (2), similarly to the adhesive (1), other components other than the polymer (X'), the compound (Y') and the active energy ray polymerization initiator (P) (for example, a crosslinking agent, a sensitizer, a diluent, tackifying agent) agent, softener, filler, stabilizer, pigment, dye, etc.) may be further contained. The description of the other components (other optional components) in the adhesive (2) is the same as that of the other components (other optional components) in the adhesive (1).

The said adhesive agent (2) can be manufactured conveniently by mixing and stirring a polymer (X'), a compound (Y'), and other optional components (active energy ray polymerization initiator (P) and other arbitrary components).

[PVA Film]

The adhesive of this invention is for adhering the film (PVA film) containing polyvinyl alcohol, and a base material. As polyvinyl alcohol (PVA) which a PVA film contains, the thing obtained by saponifying the polyvinyl ester obtained by superposing|polymerizing a vinyl ester is mentioned. Polyvinyl ester may be obtained by polymerizing only vinyl ester, or may be obtained by copolymerizing vinyl ester and another monomer copolymerizable therewith, but one obtained by polymerizing only vinyl ester is preferable. Although only 1 type may be used for the said vinyl ester and may use 2 or more types together, it is preferable to use only 1 type.

Examples of the vinyl ester include vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, isopropenyl acetate, and the like. . As said vinyl ester, the compound which has a vinyloxycarbonyl group (H2C=CH _- O-CO-) in a molecule|numerator from points, such as the ease of manufacture of PVA, easiness of acquisition, cost, etc., is preferable, and vinyl acetate is more desirable.

As another monomer copolymerizable with the vinyl ester, for example, α-olefin having 2 to 30 carbon atoms, (meth)acrylic acid, (meth)acrylate, (meth)acrylic acid ester, (meth)acrylamide, (meth)acryl Amide derivatives, N-vinylamide, vinyl ether, vinyl cyanide such as (meth)acrylonitrile, vinyl halide, allyl compound, maleic acid, maleic acid salt, maleic acid ester, maleic acid anhydride, itaconic acid, itaconic acid salt , itaconic acid ester, acid anhydride of itaconic acid, vinylsilyl compounds such as vinyl trimethoxysilane, unsaturated sulfonic acid, unsaturated sulfonic acid salt, and the like.

As said C2-C30 alpha-olefin, ethylene, propylene, 1-butene, isobutene, etc. are mentioned, for example.

As said (meth)acrylic acid ester, For example, (meth)methyl acrylate, (meth)ethyl acrylate, (meth)acrylic acid n-propyl, (meth)acrylic acid i-propyl, (meth)acrylic acid n-butyl, (meth)acrylic acid ester, ) Acrylic acid i-butyl, (meth)acrylic acid t-butyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid dodecyl, (meth)acrylic acid octadecyl, etc. are mentioned.

Examples of the (meth)acrylamide derivative include N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, diacetone (meth)acrylamide, (meth)acrylamide-propanesulfonic acid or its salt, (meth)acrylamide propyldimethylamine or its salt, N-methylol (meth)acrylamide, its derivative(s), etc. are mentioned.

Examples of the N-vinylamide include N-vinylformamide, N-vinylacetamide, and N-vinylpyrrolidone.

Examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl. Ether, stearyl vinyl ether, etc. are mentioned.

As said vinyl halide, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, etc. are mentioned, for example.

As said allyl compound, allyl acetate, allyl chloride, etc. are mentioned, for example.

As an upper limit of the ratio of the structural unit derived from the said other monomer in the said polyvinyl ester, 15 mol% is preferable with respect to the number of moles of all the structural units constituting the polyvinyl ester, more preferably 10 mol%, and 5 mol % is more preferable.

Although it is preferable that graft copolymerization is not carried out as said PVA, as long as it exists in the range which does not impair the effect of this invention significantly, what modified|denatured with the monomer which can graft copolymerize may be sufficient. The said graft copolymerization may be performed to polyvinyl ester, and may be performed to PVA obtained by saponifying polyvinyl ester.

Examples of the graft copolymerizable monomer include unsaturated carboxylic acids, derivatives of unsaturated carboxylic acids, unsaturated sulfonic acids, derivatives of unsaturated sulfonic acids, and α-olefins having 2 to 30 carbon atoms. Only 1 type may be used for the monomer which can be graft copolymerized, and may use 2 or more types together. It is preferable that the ratio of the structural unit derived from the monomer which can be graft-copolymerized in polyvinyl ester or PVA is 5 mol% or less with respect to the mole number of all the structural units which comprise polyvinyl ester or PVA.

A part of the hydroxyl groups which the said PVA has may be bridge|crosslinked. Moreover, a part of the hydroxyl group which the said PVA has may react with aldehyde compounds, such as acetaldehyde and butylaldehyde, etc., and may form the acetal structure.

As a lower limit of the saponification degree of PVA, from a viewpoint from which the heat-and-moisture resistance of a PVA film becomes favorable, 99.0 mol% is preferable, 99.8 mol% is more preferable, and 99.9 mol% is still more preferable. Here, "the degree of saponification of PVA" is a value measured according to JIS-K6726 (1994), and among the structural units of PVA, a structural unit that can be converted into a vinyl alcohol unit by saponification (typically a vinyl ester unit) and It means the ratio (mol%) for which the number of moles of the said vinyl alcohol unit occupies with respect to the total number of moles of a vinyl alcohol unit.

Although the polymerization degree in particular of the said PVA is not restrict|limited, As for the upper limit, 10,000 is preferable, 8,000 is more preferable, and 5,000 is more preferable. On the other hand, as the lower limit of the polymerization degree of the PVA, 1,000 is preferable, 1,500 is more preferable, and 2,000 is still more preferable. When the polymerization degree of the said PVA is below the said upper limit, the raise of the manufacturing cost of PVA can be suppressed, and the process passability at the time of film forming improves. On the other hand, when the polymerization degree of the said PVA is more than the said minimum, for example, when a PVA film is processed into a polarizing film as mentioned later, each performance, such as polarization|polarized-light performance, improves. Here, "the degree of polymerization of PVA" means the average degree of polymerization measured according to description of JIS-K6726 (1994).

As an upper limit of the content rate of PVA in a PVA film, 100 mass % is preferable. On the other hand, as a lower limit of the content rate of the said PVA, 50 mass % is preferable, 80 mass % is more preferable, and its 85 mass % is still more preferable.

As another component which the PVA film may contain, a plasticizer, surfactant, antioxidant, a cryoprotectant, a pH adjuster, a masking agent, a coloring inhibitor, an oil agent etc. are mentioned, for example.

The said plasticizer aims at improving the handleability and stretchability of a PVA film, etc. Although it does not specifically limit as a plasticizer, Polyhydric alcohol is preferable. Examples of the polyhydric alcohol include ethylene glycol, glycerin, propylene glycol, diethylene glycol, diglycerin, triethylene glycol, tetraethylene glycol, and trimethylolpropane. Among them, the stretchability of the PVA film is higher. Since it becomes favorable, glycerol is more preferable. A plasticizer may use only 1 type, and may use 2 or more types together.

As an upper limit of content of the plasticizer with respect to 100 mass parts of PVA in a PVA film, 20 mass parts is preferable, 17 mass parts is more preferable, and 14 mass parts is still more preferable. On the other hand, as a minimum of content of the said plasticizer, 3 mass parts is preferable, 5 mass parts is more preferable, 7 mass parts is still more preferable. When content of the said plasticizer is below the said upper limit, the handleability of a PVA film improves. On the other hand, when content of the said plasticizer is more than the said minimum, the stretchability of a PVA film improves.

The said surfactant aims at improving film forming property and suppressing generation|occurrence|production of the thickness nonuniformity of a PVA film, etc. when manufacturing a PVA film using the film forming undiluted|stock solution mentioned later. Although the kind of surfactant is not specifically limited, From a viewpoint of film forming property, an anionic surfactant or a nonionic surfactant is preferable, and a nonionic surfactant is more preferable. Surfactant may use only 1 type, and may use 2 or more types together.

Examples of the anionic surfactant include carboxylic acid type surfactants such as potassium laurate, sulfuric acid ester type surfactants such as octyl sulfate, and sulfonic acid type surfactants such as dodecylbenzenesulfonate. .

As a nonionic surfactant, For example, alkyl ether type surfactants, such as polyoxyethylene oleyl ether, alkylphenyl ether type surfactants, such as polyoxyethylene octylphenyl ether, alkylester types, such as polyoxyethylene laurate Surfactants, alkylamine surfactants such as polyoxyethylene laurylamino ether, alkylamide surfactants such as polyoxyethylene lauric acid amide, polypropylene glycol ether surfactants such as polyoxyethylene polyoxypropylene ether; Alkanolamide type surfactants, such as lauric acid diethanolamide and oleic acid diethanolamide, and allylphenyl ether type surfactants, such as polyoxyalkylene allylphenyl ether, etc. are mentioned.

As an upper limit of content of surfactant with respect to 100 mass parts of PVA in a PVA film, 0.5 mass part is preferable and 0.3 mass part is more preferable. On the other hand, as a lower limit of content of the said surfactant, 0.01 mass part is preferable and 0.02 mass part is more preferable. When content of the said surfactant is below the said upper limit, the handleability of a PVA film improves. On the other hand, when content of the said surfactant is more than the said minimum, film forming property improves.

Although it does not specifically limit as an upper limit of the thickness of a PVA film, 50 micrometers is preferable, 45 micrometers is more preferable, and 30 micrometers is still more preferable. On the other hand, although it does not specifically limit as the minimum of the thickness of a PVA film, From a viewpoint of manufacturing a PVA film smoothly, 3 micrometers is preferable.

[Method for producing PVA film]

The manufacturing method in particular of a PVA film is not restrict|limited, The manufacturing method in which the thickness and width of the film after film forming become more uniform can be employ|adopted preferably, For example, the said PVA which comprises a PVA film, and if necessary further One or two or more of a plasticizer, a surfactant, an antioxidant, an anti-freezing agent, a pH adjuster, a masking agent, an anti-coloring agent, an emulsion, and the like are dissolved in a liquid medium, PVA, and additionally a plasticizer, a surfactant It can be prepared using a film forming undiluted solution in which PVA is melted and containing one or two or more of an activator, an antioxidant, an anti-freezing agent, a pH adjuster, a masking agent, an anti-coloring agent, an emulsion, and the like. When the said film forming undiluted|stock solution contains arbitrary components, such as a plasticizer and surfactant, it is preferable that these components are mixed uniformly.

Examples of the liquid medium include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, Trimethylolpropane, ethylenediamine, diethylenetriamine, etc. are mentioned. Among these, water is preferable in terms of a small load on the environment and a point of recoverability. As for the said liquid medium, only 1 type may be used and 2 or more types may be used together.

The content ratio in the film forming undiluted solution of volatile components such as a liquid medium removed by volatilization or evaporation during film forming (volatile fraction of the film forming undiluted solution) varies depending on the film forming method and film forming conditions, etc., but the upper limit thereof is 95% by mass. Preferably, 90 mass % is more preferable, and 85 mass % is still more preferable. On the other hand, as a lower limit of the volatile matter rate of the said film forming undiluted|stock solution, 50 mass % is preferable, 55 mass % is more preferable, and its 60 mass % is still more preferable. When the volatile fraction of the film forming undiluted solution is equal to or less than the upper limit, the concentration of the film forming undiluted solution does not become too low, and production of an industrial PVA film becomes easy. On the other hand, when the volatile fraction of the undiluted film forming solution is equal to or greater than the lower limit, the viscosity of the undiluted film forming solution does not become excessively high, and filtration and defoaming at the time of preparing the film forming undiluted solution are smoothly performed. .

As a film forming method at the time of forming a PVA film using the said film forming undiluted|stock solution, for example, a cast film forming method, an extrusion film forming method, a wet film forming method, a gel film forming method, etc. are mentioned, The thickness and width are uniform, and physical property The cast film forming method and the extrusion film forming method are preferable at the point from which a favorable PVA film is obtained. The said film forming method may employ|adopt only 1 type, and may employ|adopt it in combination of 2 or more type. The film formed into a film can be dried or heat-processed as needed.

As an example of a specific manufacturing method of a PVA film, for example, a T-type slit die, a hopper plate, an I-die, a lip coater die, etc. are used, and the rotating heated first roll ( or belt) uniformly discharged or cast on the peripheral surface of the first roll (or belt), volatile components are evaporated from one surface of the film discharged or cast on the peripheral surface of the belt, and dried, and then on the downstream side A method of further drying on the circumferential surface of one or a plurality of rotating heated rolls arranged in the there is. You may perform drying by the heated roll and drying by a hot-air drying apparatus combining suitably.

By the above manufacturing method, the PVA film which has not been substantially extended|stretched (it did not go through an extending|stretching process) can be obtained easily. Although this PVA film can be adhered to a base material as it is using the said adhesive agent, in this invention, it is preferable that the PVA film which the said adhesive agent adheres to a base material is a stretched PVA film (stretched polyvinyl alcohol film), especially It is preferable that they are optical films, such as a polarizing film and retardation film.

[Method for producing polarizing film]

The manufacturing method of a polarizing film is not specifically limited, For example, with respect to the PVA film which has not been substantially stretched, swelling, dyeing|staining, extending|stretching, and, if necessary, further crosslinking treatment, fixing treatment, drying, heat treatment, etc. A method of carrying out is mentioned. In this case, the order in particular of each process, such as swelling, dyeing|staining, a crosslinking process, extending|stretching, a fixing process, is not restrict|limited, One or two or more processes may be implemented simultaneously. Moreover, one or two or more of each process can also be performed twice or more. In addition, when adding a dichroic dye to a film forming undiluted|stock solution in a film forming process, a dyeing process can be abbreviate|omitted.

(swelling)

Swelling can be performed by immersing the said PVA film in water. It is not limited to pure water as this water, The aqueous solution which various components melt|dissolved may be sufficient, and the mixture of water and an aqueous medium may be sufficient. As this aqueous medium, the thing similar to the liquid medium illustrated in the said film forming undiluted|stock solution is mentioned, for example.

As an upper limit of the temperature of the water at the time of immersing a PVA film in water, 40 degreeC is preferable, 38 degreeC is more preferable, and 35 degreeC is still more preferable. On the other hand, as a lower limit of the temperature of the said water, 20 degreeC is preferable, 22 degreeC is more preferable, and 25 degreeC is still more preferable. Moreover, as an upper limit of time to immerse a PVA film in water, 5 minutes are preferable and 3 minutes are more preferable. On the other hand, as a lower limit of the time to be immersed in the said water, 0.5 minute is preferable and 1 minute is more preferable.

(dyeing)

Dyeing can be performed by immersing the said PVA film in the aqueous solution containing a dichroic dye. As said dichroic dye, an iodine-type dye, a dichroic organic dye, etc. are mentioned.

As said iodine-type pigment|dye, I ₃ ^- , I ₅ ^- , etc. are mentioned, for example. These iodine-type pigment|dye can be obtained by making iodine ( _I2 ) and potassium iodide contact, for example.

As said dichroic organic dye, For example, Direct Black 17, 19, 154; Direct Brown 44, 106, 195, 210, 223; Direct Red 2, 23, 28, 31, 37, 39, 79, 81, 240, 242, 247; Direct Blue 1, 15, 22, 78, 90, 98, 151, 168, 202, 236, 249, 270; Direct Violet 9, 12, 51, 98; Direct Green 1, 85 ; Direct Yellow 8, 12, 44, 86, 87; Direct Orange 26, 39, 106, 107, etc. are mentioned.

As a dichroic dye, an iodine-type dye is preferable from a viewpoint of handleability, availability, polarization|polarized-light performance, etc. These dichroic dyes may be used individually by 1 type, may use 2 or more types together, for example, an equilibrium mixture may be sufficient as I ₃ ^- and I ₅ ^- .

The density|concentration of the dichroic dye in the aqueous solution containing the said dichroic dye can be set suitably according to the kind etc. of the dichroic dye to be used, For example, it can be 0.001 mass % or more and 1 mass % or less. When an iodine-potassium iodide aqueous solution is used as an aqueous solution containing a dichroic dye, since the iodine-based dye can be efficiently adsorbed to the PVA film, the concentration of iodine (I ₂ ) used is 0.01 mass % or more and 1.0 Mass % or less is preferable, and 0.01 mass % or more and 10 mass % or less are preferable as a density|concentration of potassium iodide (KI) used.

As an upper limit of the temperature of the aqueous solution containing the said dichroic dye, 50 degreeC is preferable and 40 degreeC is more preferable. On the other hand, as a lower limit of the temperature of the said aqueous solution, 20 degreeC is preferable and 25 degreeC is more preferable. By carrying out the temperature of the said aqueous solution in the said range, a dichroic dye can be made to adsorb|suck to a PVA film efficiently.

(bridge)

Crosslinking can be performed by immersing the said PVA film in the aqueous solution containing a crosslinking agent. By this bridge|crosslinking, even when extending|stretching at a relatively high temperature and wet, it can prevent effectively that PVA elutes into water. For this reason, it is preferable to perform bridge|crosslinking before extending|stretching.

As said crosslinking agent, a boron compound is mentioned, for example, As this boron compound, borate, such as boric acid and borax, etc. are mentioned, for example. Only 1 type may be used for this crosslinking agent, and may use 2 or more types together. Moreover, the aqueous solution containing a crosslinking agent may contain auxiliary agents, such as potassium iodide.

As an upper limit of the density|concentration of the crosslinking agent in the aqueous solution containing the said crosslinking agent, 15 mass % is preferable and 7 mass % is more preferable. On the other hand, as a lower limit of the density|concentration of the said crosslinking agent, 1 mass % is preferable and 2 mass % is more preferable. As an upper limit of the temperature of the aqueous solution containing the said crosslinking agent, 50 degreeC is preferable and 40 degreeC is more preferable. On the other hand, as a lower limit of the temperature of the said aqueous solution, 20 degreeC is preferable and 25 degreeC is more preferable.

(Former Yeon-shin)

Separately from the stretching process mentioned later, a PVA film can be extended|stretched simultaneously with one or two or more of processes, such as swelling, dyeing|staining, crosslinking. By performing such extending|stretching (total extending|stretching), it can prevent that wrinkles arise in a PVA film. Based on the original length of the PVA film before stretching from the viewpoint of polarization performance of the polarizing film obtained, etc., the draw ratio of all stretching is preferably 4 times or less, more preferably 3.5 times or less, and more preferably 1.5 times or more. .

Moreover, regarding the draw ratio in each process, as an upper limit of the draw ratio at the time of swelling, 3 times are preferable, 2.5 times are more preferable, and 2.3 times are more preferable. On the other hand, as a lower limit of the said draw ratio, 1.1 times are preferable, 1.2 times are more preferable, and 1.4 times are more preferable.

As an upper limit of the draw ratio at the time of dyeing, 2 times are preferable, 1.8 times are more preferable, and 1.5 times are more preferable. On the other hand, as a lower limit of the said draw ratio, 1.1 times is preferable.

As an upper limit of the draw ratio at the time of bridge|crosslinking, 2 times are preferable, 1.5 times are more preferable, and 1.3 times are more preferable. On the other hand, as a lower limit of the said draw ratio, 1.05 time is preferable.

(stretch)

The stretching method in particular at the time of extending|stretching a PVA film is not restrict|limited, Although a wet stretching method or a dry stretching method can be employ|adopted, a wet stretching method is preferable from a viewpoint of improving the uniformity of the thickness of the width direction of the polarizing film obtained. .

When adopting the wet stretching method, stretching may be performed in an aqueous solution containing a boron compound, or stretching may be performed in an aqueous solution containing the dichroic dye or in a fixed treatment bath described later. As a boron compound, borate, such as boric acid and borax, etc. are mentioned, for example, 1 type(s) or 2 or more types of these can be used. Among these, it is preferable to extend|stretch in the aqueous solution containing a boron compound, and it is more preferable to extend in the aqueous solution containing a boric acid. In this case, as an upper limit of the density|concentration of the boric acid in the aqueous solution containing the said boric acid, 6 mass % is preferable, 5 mass % is more preferable, 4 mass % is still more preferable. On the other hand, as a lower limit of the density|concentration of the said boric acid, 0.5 mass % is preferable, 1 mass % is more preferable, and its 1.5 mass % is still more preferable. Moreover, the aqueous solution containing the said boron compound may contain potassium iodide. In this case, as a density|concentration of potassium iodide in the aqueous solution containing the said boron compound, 0.01 mass % or more and 10 mass % or less are preferable.

When employing the dry stretching method, extending|stretching may be performed at room temperature, you may extend|stretch, heating, and after making a PVA film absorb, you may extend|stretch.

As an upper limit of the temperature at the time of extending|stretching a PVA film in the said extending|stretching, 90 degreeC is preferable, 80 degreeC is more preferable, and its 70 degreeC is still more preferable. On the other hand, as a lower limit of the said temperature, 30 degreeC is preferable, 40 degreeC is more preferable, and 50 degreeC is still more preferable.

As a minimum of the draw ratio of the PVA film in the said extending|stretching, 1.2 times are preferable, 1.5 times are more preferable, and 2 times are more preferable.

Moreover, the total draw ratio (magnification multiplied by the draw ratio of each draw) including the draw ratio of the said all stretch is 5.5 times or more based on the original length of the PVA film before extending|stretching from a viewpoint, such as polarization performance of the polarizing film obtained. It is preferable, 5.7 times or more is more preferable, 5.8 times or more are still more preferable, and 5.9 times or more are especially preferable. Although it does not restrict|limit especially as an upper limit of the said total draw ratio, 8 times is preferable.

As extending|stretching of a PVA film, uniaxial stretching is preferable from a viewpoint of the performance of the polarizing film obtained. There is no restriction|limiting in particular in the direction of this uniaxial stretching, The uniaxial stretching to the longitudinal direction in a long PVA film, and transverse uniaxial stretching are employable. Among these, uniaxial stretching to a longitudinal direction is preferable at the point from which the polarizing film which is more excellent in polarization|polarized-light performance is easy to be obtained. Uniaxial stretching to the said longitudinal direction can be implemented by changing the peripheral speed between each roll, for example using the extending apparatus provided with the some roll mutually parallel. On the other hand, the transverse uniaxial stretching may be performed using a tenter type stretching machine.

(fixed processing)

A fixed process can be implemented by immersing the said PVA film in a fixed process bath. Thereby, adsorption|suction of the dichroic dye to the said PVA film can be made strong. A fixation process will not be specifically limited if it is after dyeing, A fixation process may be performed before extending|stretching, a fixation process may be performed simultaneously with extending|stretching, and a fixed process may be performed after extending|stretching.

As said fixed treatment bath, the aqueous solution containing a boron compound is mentioned, for example, As this boron compound, borate, such as boric acid and borax, etc. are mentioned, for example. Only 1 type may be used for this boron compound, and 2 or more types may be used together. As an upper limit of the density|concentration of the boron compound in the aqueous solution containing the said boron compound, 15 mass % is preferable and 10 mass % is more preferable. On the other hand, as a lower limit of the density|concentration of the said boron compound, 2 mass % is preferable and 3 mass % is more preferable.

As an upper limit of the temperature of the said fixed treatment bath, 60 degreeC is preferable and 40 degreeC is more preferable. On the other hand, as a lower limit of the temperature of the said fixed treatment bath, 15 degreeC is preferable and 25 degreeC is more preferable.

(dry)

After extending|stretching and performing a fixed process further as needed, a polarizing film can be obtained by drying. Although drying conditions in particular are not restrict|limited, As a minimum of a drying temperature, 30 degreeC is preferable and 50 degreeC is more preferable. On the other hand, as an upper limit of drying temperature, 150 degreeC is preferable and 130 degreeC is more preferable. By carrying out drying temperature in the said range, the dimensional stability of a polarizing film improves.

[Other PVA Film]

In the present invention, as PVA films other than the above-described polarizing film and retardation film among the PVA films that the adhesive adheres to the substrate, for example, optical films other than polarizing films and retardation films, conductive films, photosensitive films, protective films, A release film, a rust preventive film, a coverlay film, a transfer film, an abrasive film, a wind film, a decorative film, an adhesive film, the film for vibration damping steel plates, a biodegradable film, an antibacterial film, etc. are mentioned. Examples of the optical film other than the polarizing film and the retardation film include an antireflection film, an orientation film, a polarizing layer protective film, a viewing angle improvement film, a brightness enhancement film, an electromagnetic wave shielding film, a light shielding film, an infrared blocking film, an ultraviolet blocking film, a lens filter, an optical low pass filter (OLPF) film, a weather resistant film, etc. are mentioned.

[write]

In this invention, there is no restriction|limiting in particular in the base material with which the said adhesive agent adheres to a PVA film, Although a film, what has various shapes, such as a hollow or solid block body, are mentioned, A film is especially preferable. Examples of the film include ionomer, polyethylene, cellulose, triacetyl cellulose (TAC), (meth)acrylic polymer, alicyclic structure-containing polymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polypropylene, and films made of polymers such as polyester, polycarbonate, polystyrene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-methacrylic acid copolymer, and nylon. Here, the (meth)acrylic polymer has a lactone ring unit, maleic anhydride unit, N-substituted or unsubstituted maleimide unit, glutaric anhydride unit, N-substituted or unsubstituted glutalimide unit, etc. in the main chain. The introduced modified (meth)acrylic polymer may be used. Among these, a film containing triacetyl cellulose, a film containing a (meth)acrylic polymer, polyester containing A film or a film comprising an alicyclic structure-containing polymer is preferred. As an upper limit of the content rate of the said polymer in the said film, 100 mass % is preferable. On the other hand, as a lower limit of the said content rate, 50 mass % is preferable, 80 mass % is more preferable, and 85 mass % is still more preferable.

When the said base material is a film, although the thickness is not specifically limited, As for the upper limit, 200 micrometers is preferable and 80 micrometers is more preferable. On the other hand, as a lower limit of the said thickness, 5 micrometers is preferable and 10 micrometers is more preferable. When the said thickness is below the said upper limit, it can suppress that the thickness of the adhesive agent obtained increases unnecessarily. On the other hand, when the said thickness is more than the said minimum, the intensity|strength of the adhesive agent obtained improves.

Even when a base material is not a film, the base material containing the same thing as the said polymer in the case where a base material is a film can be used preferably. In this case, as an upper limit of the content rate of the said polymer in a base material, 100 mass % is preferable. On the other hand, as a lower limit of the said content rate, 50 mass % is preferable, 80 mass % is more preferable, and 85 mass % is still more preferable. Moreover, the base material may contain a metal, a fiber, a fabric, synthetic leather, etc.

[Use of adhesive]

As a use of the adhesive agent of this invention, The use which adhere|attaches the above-mentioned polarizing film or retardation film, and a protective film (manufacturing use of a polarizing plate or retardation plate); Adhesion of a PVA film to a metal, synthetic resin, rubber, etc. in manufacture of an electronic element, an electronic device, etc.; adhesion of materials in the field of civil engineering and construction, adhesion of fibers, fabrics, synthetic leather, etc. in coverings; Adhesion of food packaging, etc. are mentioned, In the manufacturing use of a polarizing plate or retardation plate, especially, it is especially useful in the manufacturing use of a polarizing plate.

ADVANTAGE OF THE INVENTION According to the adhesive agent of this invention, it has high adhesive strength in adhesion|attachment of a PVA film and a base material. As a specific adhesive strength, as for the peel adhesive strength of the PVA film and a base material after hardening of the said adhesive agent, 2.5 N/25 mm is preferable, as for the lower limit, 3 N/25 mm is more preferable, 3.75 N/25 mm is more preferably.

<Adhesive>

Next, embodiment of the adhesive agent of this invention is described. The adhesive body 1 of FIG. 1 is equipped with the PVA film 2, the base material 4, and the adhesive bond layer 3 arrange|positioned between the said PVA film 2 and the base material 4. This adhesive bond layer 3 is formed from the said adhesive agent.

[Adhesive layer]

The adhesive bond layer 3 is formed of the said adhesive agent. Specifically, it can form by irradiating an active energy ray with respect to the said adhesive agent. The adhesive layer 3 may contain an additive according to the use of the adhesive body 1 .

As an upper limit of the thickness of the adhesive bond layer 3, 500 micrometers is preferable, 50 micrometers is more preferable, 20 micrometers is still more preferable, and 10 micrometers is especially preferable. On the other hand, as a lower limit of the said thickness, 100 nm is preferable, 300 nm is more preferable, and 500 nm is still more preferable. When the thickness of the said adhesive bond layer 3 is below the said upper limit, it can suppress that the thickness of the adhesive body 1 obtained increases unnecessarily. On the other hand, when the said thickness is more than the said minimum, the adhesive strength of the PVA film 2 and the base material 4 improves.

<Method for producing an adhesive>

The adhesive body (1) is prepared by the step of obtaining a laminate in which the PVA film (2), the adhesive agent, and the substrate (4) are arranged in this order (laminate manufacturing process), and after the laminate manufacturing process, the active energy It can manufacture by the manufacturing method provided with the process (irradiation process) of irradiating a wire|line to the said adhesive agent.

[Laminate manufacturing process]

A laminate manufacturing process WHEREIN: The said laminated body is manufactured. The manufacturing method of this laminate is not particularly limited as long as a laminate in which the PVA film, the adhesive, and the substrate are arranged in this order is obtained, but since the laminate is obtained more conveniently, the adhesive is applied to the surface of the PVA film, and the substrate A method of laminating the PVA film and the substrate after applying the adhesive to one or both surfaces of the substrate is preferred. The coating method when applying the adhesive to one or both of the surface of the PVA film and the surface of the substrate is not particularly limited, and for example, die coat, roll coat, air knife coat, gravure roll coat, doctor roll coat, Methods, such as a doctor knife coat, a curtain flow coat, a spray, a wire bar, a rod coat, immersion, and brush application, are mentioned.

Moreover, as a manufacturing method of the said laminated body, after overlapping a PVA film and a base material other than the above, the method of permeating the said adhesive agent between both can also be employ|adopted.

Moreover, you may pressurize the obtained laminated body with a roll etc. In this case, as a material of the said roll, a metal, rubber|gum, etc. are mentioned, for example. The same material may be sufficient as the roll by the side of a PVA film, and the roll by the side of a base material may be sufficient as a different material.

[Investigation process]

An irradiation process WHEREIN: An active energy ray is irradiated to the said adhesive agent which is uncured in the said laminated body. As this active energy ray, it can select suitably according to the kind of active energy ray-curable group contained in the said adhesive agent. As said active energy ray, an electron beam, a proton ray, a neutron beam, etc. other than electromagnetic waves, such as an ultraviolet-ray, infrared ray, X-ray, and gamma ray, are mentioned, for example. Among these, an ultraviolet-ray or an electron beam is preferable from a viewpoint of a curing rate, the availability of an irradiation apparatus, price, etc., and an ultraviolet-ray is more preferable.

The active energy ray can be irradiated using a known device. When using ultraviolet rays as the active energy ray, high-pressure mercury lamps, ultra-high pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, LEDs, etc. that emit light in a wavelength range of 450 nm or less can be used. Moreover, when using the electron beam EB as an active energy ray, 0.1 MeV or more and 10 MeV or less as an acceleration voltage, and 1 kGy or more and 500 kGy or less as an irradiation dose are preferable.

As a lower limit of the accumulated light amount of the said active energy ray, 10 mJ/cm<2> is preferable and 30 mJ/cm<2> is more preferable. On the other hand, as an upper limit of the accumulated light amount of an active energy ray, 20,000 mJ/cm<2> is preferable and 5,000 mJ/cm<2> is more preferable. When the amount of accumulated light of an active energy ray is more than the said minimum, the curing rate of the said adhesive agent and the adhesive strength after hardening improve. On the other hand, when the amount of accumulated light of an active energy ray is below the said upper limit, irradiation time can be made into an appropriate range, and productivity improves.

Curing may be accelerated|stimulated by heating as needed during or after irradiation with active energy ray to the said adhesive agent. As a lower limit of this heating temperature, 40 degreeC is preferable and 50 degreeC is more preferable. On the other hand, as an upper limit of heating temperature, 130 degreeC is preferable and 100 degreeC is more preferable. When heating temperature is more than the said lower limit, the accelerating effect of hardening improves. On the other hand, when heating temperature is below the said upper limit, deterioration of the said adhesive agent is suppressed.

An adhesive bond layer is formed by hardening of the said adhesive agent, and the said adhesive body is obtained.

<Other embodiments>

It should be considered that the embodiment disclosed this time is illustrative and not restrictive in all respects. The scope of the present invention is not limited to the configuration of the above-described embodiment, is indicated by the claims, and it is intended that all changes within the meaning and scope equivalent to the claims are included.

The said adhesive body may have a some adhesive bond layer. For example, in the PVA film, an adhesive layer is also provided on the side opposite to the side on which the adhesive layer is formed as described above, and a separate substrate is laminated on the side opposite to the PVA film of this adhesive layer, so that the substrate / adhesive You may have the structure of layer / PVA film / adhesive bond layer / base material, or you may have the structure of PVA film / adhesive layer / base material / adhesive layer / PVA film.

Example

Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

<Preparation of adhesive>

[Synthesis of (meth)acrylic polymer (P-1)]

100 ml of toluene was put into a 300 ml flask which was dried and purged with nitrogen, and while stirring, 0.78 ml (2.86 mmol) of 1,1,4,7,10,10-hexamethyltriethylenetetramine as a Lewis base and 12.7 ml of a 0.450 mol/L toluene solution of isobutylbis(2,6-di-t-butyl-4-methylphenoxy)aluminum as a tertiary organoaluminum compound were sequentially added. This solution is cooled to -20 degreeC, 2.00 ml of a 1.30 mol/L cyclohexane solution of sec-butyllithium as an organolithium compound is added, and 1,1-dimethylpropane-1,3-diol as an active energy ray-curable monomer is added. 3.58 ml of a mixture of 2.47 ml (10.4 mmol) of dimethacrylate and 1.11 ml (10.4 mmol) of methyl methacrylate as a mono(meth)acrylic acid ester was added at once to initiate anionic polymerization (first polymerization process). 10 minutes after the start of the anionic polymerization, the polymerization reaction liquid changed from yellow to colorless. This polymerization reaction solution was further stirred for 10 minutes.

Next, while stirring this polymerization reaction liquid at -20 degreeC, 2.22 ml (20.8 mmol) of methyl methacrylate as monomethacrylic acid ester are added all at once, and 100 minutes after that, n-butyl acrylic acid as a monoacrylic acid ester is added. Anionic polymerization was performed by further adding 37.4 ml (260 mmol) at a rate of 1 ml/min (second polymerization step).

Then, 10.0 ml of methanol was added at -20 degreeC, stirring this polymerization reaction liquid, and anionic polymerization was stopped. The obtained solution was poured into 1 liter of methanol, and the (meth)acrylic-type polymer (P-1) was obtained by collect|recovering a deposit. Mn of the (meth)acrylic polymer (P-1) was 24,700, and Mw/Mn was 1.21.

Among each compound used for preparation of an adhesive agent, things other than the said (meth)acrylic-type polymer (P-1) are shown below.

[Compound (Y)]

M-1: acrylic acid tetrahydrofurfuryl ("Viscoat 150" manufactured by Osaka Organic Co., Ltd.)

M-2: 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate ("Celoxide 2021P" manufactured by Daicel Chemical Industry Co., Ltd.)

M-3: 3-ethyl-3-hydroxymethyloxetane (“OXT-101” manufactured by Dong-A Synthesis Co., Ltd.)

M-4: 3-ethyl-3-acryloyloxymethyloxetane ("OXE-10" manufactured by Osaka Organic Co., Ltd.)

L-1: tris (2-hydroxyethyl) isocyanurate triacrylate (“M-315” manufactured by Dong-A Synthesis Co., Ltd.)

[Active energy ray polymerization initiator (P)]

Radical polymerization initiator (R-1): 1-hydroxycyclohexylphenyl ketone ("IRGACURE 184" manufactured by BASF)

Cationic polymerization initiator (C-1): 50 mass% solution of diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate in propylene carbonate (“CPI-100P” manufactured by San Apro)

[Example 1]

<Production of adhesive>

In a container equipped with a sealable stirring device, 14 parts by mass of the (meth)acrylic polymer (P-1), 43 parts by mass of (M-1) as compound (Y), 33 parts by mass of (M-2) and (L) -1) 5 parts by mass, 3 parts by mass of (R-1) as a radical polymerization initiator (R), and 2 parts by mass of (C-1) as a cationic polymerization initiator (C) are added, and the adhesive (A) is stirred for 24 hours. -1) was prepared.

<Production of adhesive (polarizing plate)>

Using a polymethyl methacrylate film (manufactured by Kuraray Co., Ltd.) having a thickness of 50 µm as a substrate, and using a bar coater on one side of the polymethyl methacrylate film, the adhesive (A-1) was applied to a thickness of 2 It coated so that it might become micrometer. Next, a 10 µm-thick polarizing film (prepared by performing dyeing and stretching of a PVA film with an iodine dye) was superposed on the substrate through this adhesive. Thereafter, the adhesive (A-1) was coated to a thickness of 2 µm using a bar coater on the side of the polarizing film that was not in contact with the adhesive, and as a separate substrate, polymethacrylic having a thickness of 50 µm A methyl acid film (manufactured by Kuraray Co., Ltd.) was overlapped with the polarizing film through the adhesive. Thus, the laminated body which has the laminated constitution of polymethyl methacrylate film/adhesive agent/polarizing film/adhesive agent/polymethyl methacrylate film was pressed using the roller.

Thereafter, using an ultraviolet irradiation device (a metal halide lamp manufactured by GS YUASA Co., Ltd. was used as the lamp), ultraviolet rays were irradiated to the laminate so that the amount of accumulated light was 700 mJ/cm 2 . In addition, about this accumulated light amount, it measured using the UV measuring instrument (GS YUASA Corporation). After ultraviolet irradiation, the polarizing plate as an adhesive body was obtained by making it stand still at the temperature of 23 degreeC, and 50% of a relative humidity for 24 hours. In addition, about the size of a polarizing plate and a laminated body, it was set as width 10 mm x length 50 mm for what is for evaluating a curing rate and peel adhesive strength, and set it as width 50 mm x length 50 mm about what is for evaluating a deflection amount.

<Evaluation>

About the said polarizing plate, each evaluation was performed with the following procedure. In addition, about evaluation of a curing rate, the laminated body immediately after ultraviolet irradiation in manufacture of the said adhesive body (polarizing plate) was used.

[Crosslinking density after curing and storage modulus at 150°C]

The adhesive agent was apply|coated on the base film which carried out the release process, and ultraviolet-ray was irradiated to this using the ultraviolet irradiation apparatus (GS YUASA Co., Ltd. metal halide lamp was used as a lamp|ramp) so that the accumulated light amount might be 700 mJ/cm<2>. In addition, about this accumulated light amount, it measured using the UV measuring instrument (GS YUASA Corporation). After ultraviolet irradiation, after leaving still at the temperature of 23 degreeC and 50% of relative humidity for 24 hours, hardened|cured material was peeled from the base film. The sample of the cured product thus obtained was subjected to dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring apparatus (“Rheogel-E4000” manufactured by UB M Co., Ltd.). Then, at a temperature of 150°C belonging to the rubbery flat region, the storage elastic modulus (E′) is obtained, and the crosslinking density is calculated from the relationship of E′=3vRT using the value of the storage elastic modulus (E′) at 150°C. did Moreover, also in any Example and the comparative example, Tg of hardened|cured material was sufficiently smaller than 120 degreeC.

[Cure speed]

About the laminated body immediately after ultraviolet irradiation, after inserting a cut in the adhesive bond layer part with a cutter as needed, the polarizing film and one polymethyl methacrylate film were peeled by hand. The polarizing film and the polymethyl methacrylate film could not be completely peeled off because the adhesive was cured sufficiently, and the polymethyl methacrylate film was broken A (good), and the polarizing film and the polymethacrylate were insufficient because the curing of the adhesive was insufficient. The methyl acrylate film could be peeled easily, and the thing in which neither film was damaged was evaluated as B (defect).

[Peel Adhesive Strength]

After leaving the said polarizing plate still at a temperature of 23 degreeC and 50% of relative humidity for further 24 hours, using a small tensile tester, based on JIS-K6854-2 (1999), at a peeling rate of 30 mm/min and a polarizing film and one side The peeling force at the time of peeling a polymethyl methacrylate film 180 degree was measured. It was set as the converted value in the case of width 25mm by multiplying the obtained measured value by 2.5.

[Amount of Warp]

After allowing the polarizing plate to stand still for an additional 24 hours at a temperature of 23 ° C. and a relative humidity of 60%, it is placed against a smooth surface, and the distance between the smooth surface and the corner of the polarizing plate is measured for each of the four corners, The largest value was made into the amount of deflection (limit deflection amount). As this amount of deflection (limit deflection amount), 1 mm or less is preferable. These results are shown in Table 2.

[Examples 2 to 6 and Comparative Examples 1 to 4]

Adhesives (A-2) to (A-6) and (CA-1) to (CA-4) were prepared in the same manner as in Example 1, except that each compound of the kind and usage amount shown in Table 1 was used. In the adhesive (A-6), an acrylic resin acrylate ("KRAD-3611" manufactured by Negami Kogyo Co., Ltd.) (P-2) was used instead of the (meth)acrylic polymer (P-1). In addition, in the adhesives (CA-1) and (CA-2), instead of the (meth)acrylic polymer (P-1), polyether-based urethane acrylate (“Yupimer AU-2300” manufactured by Mitsubishi Chemical Corporation) (P- 3) was used. In addition, "-" in Table 1 shows that the compound is not used.

Moreover, it carried out similarly to Example 1 except having used the adhesive agent (A-2) - (A-6) and (CA-1) - (CA-4) respectively instead of the adhesive agent (A-1), and the adhesive agent (polarizing plate) was manufactured, and each evaluation similar to Example 1 was performed. These results are shown in Table 2.

As shown in Table 2, the adhesives of Examples all show high peel adhesive strength, have high adhesive strength in adhesion between a PVA film and a base material, have a fast curing rate, and can reduce warpage of a polarizing plate. On the other hand, the adhesive agent of a comparative example was inferior in peel adhesive strength, and a curing rate was slow, or the amount of curvature of a polarizing plate was large.

1: adhesive
2: PVA film
3: adhesive layer
4: description

Claims (22)

As an adhesive for adhering a film containing polyvinyl alcohol and a substrate,
A (meth)acrylic polymer (X) having an active energy ray-curable group;
contains a compound (Y) having an active energy ray-curable group other than the (meth)acrylic polymer (X);
The (meth)acrylic polymer (X) is an adhesive having a (meth)acrylic polymer block (A) having an active energy ray-curable group and a (meth)acrylic polymer block (B) having substantially no active energy ray-curable group. The method of claim 1,
The active energy ray-curable group of the (meth)acrylic polymer (X) is at least one selected from the group consisting of a group having a group represented by the following formula (1), a group having an oxirane ring, and a group having an oxetane ring. glue.
[Formula 1]

(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) 3. The method of claim 2,
The adhesive agent in which the active energy ray-curable group which the said (meth)acrylic-type polymer (X) has is group which has group represented by the said Formula (1). The method of claim 1,
The adhesive agent in which the active energy ray-curable group which the said (meth)acrylic-type polymer (X) has is group represented by following formula (2).
[Formula 2]

(Wherein, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ² and R ³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and X ¹ is an oxygen atom, a sulfur atom, or - NR ⁴ -, R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and n represents an integer of 1 to 20) The method of claim 1,
The adhesive whose content rate of the said (meth)acrylic-type polymer (X) is 1 mass % or more and 90 mass % or less. The method of claim 1,
An adhesive wherein the compound (Y) is at least one selected from the group consisting of a compound having a group represented by the following formula (3), a compound having an oxirane ring, and a compound having an oxetane ring.
[Formula 3]

(Wherein, R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, X ² represents an oxygen atom, a sulfur atom or -NR ⁶ -, and R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms) The method of claim 1,
The adhesive whose content rate of the said compound (Y) is 10 mass % or more and 99 mass % or less. The method of claim 1,
The adhesive which further contains an active energy ray polymerization initiator (P). The method of claim 1,
An adhesive having a crosslinking density of 0.4 mol/L or more and 2 mol/L or less, determined from the storage elastic modulus of a rubbery flat region obtained by measuring dynamic viscoelasticity after curing. 10. The method of claim 9,
An adhesive whose storage elastic modulus at 150°C obtained by measuring dynamic viscoelasticity after curing is 4×10 ⁶ Pa or more and 21×10 ⁶ Pa or less. The method of claim 1,
The adhesive wherein the film containing the polyvinyl alcohol is a stretched polyvinyl alcohol film. 12. The method of claim 11,
The adhesive in which the said stretched polyvinyl alcohol film is a polarizing film or retardation film. The method of claim 1,
The adhesive whose said base material is a film. 14. The method of claim 13,
The film is an adhesive comprising triacetyl cellulose, a (meth)acrylic polymer, polyester, or an alicyclic structure-containing polymer. The method of claim 1,
The adhesive whose peel adhesive strength of the film containing polyvinyl alcohol after hardening and a base material is 2.5 N/25 mm or more. An adhesive comprising a film containing polyvinyl alcohol, a substrate, and an adhesive layer disposed between the film and the substrate containing polyvinyl alcohol,
An adhesive in which the adhesive layer is formed of the adhesive according to claim 1. a step of obtaining a laminate in which a film containing polyvinyl alcohol, the adhesive according to claim 1, and a substrate are arranged in this order; and
The manufacturing method of the adhesive body provided with the process of irradiating an active energy ray to the said adhesive agent after the process of obtaining the said laminated body. delete delete delete delete delete

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