JP2016037575A - Curable sealant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable sealant excellent in curing rate and flexibility after curing.SOLUTION: The curable sealant contains: a (meth)acrylic block copolymer (A) comprising a (meth)acrylic polymer block (a) having a curable functional group represented by formula (1) and a (meth)acrylic polymer block (b) having no curable functional group; and a polymerization initiator. (Ris H or a 1-20C hydrocarbon group; Rand Rare each independently H or a 1-6C hydrocarbon group; X is O, S, or N(R); Ris H or a 1-6C hydrocarbon group; and n is an integer of 2-20.)SELECTED DRAWING: None

Description

  The present invention relates to a curable sealing agent having excellent curing speed and flexibility after curing.

  Sealing agents are used in a wide range of industrial fields such as architecture, electricity, and automobiles. There are curable and hot-melt sealants, but curable sealants have high heat resistance (high rubber elasticity at high temperatures and little change over time in elasticity caused by plastic deformation at high temperatures). It is useful in that the sealability during construction can be maintained at a high temperature for a long time. Examples of the curable sealant include silicone, urethane, polysulfide, acrylic, and butyl rubber. Examples of the hot melt type include EVA, soft vinyl chloride, and thermoplastic elastomer. In recent years, with the enhancement of functions of products, there has been a demand for better sealing performance with a sealing agent and ease of disassembly during re-construction and recycling.

  In recent years, curable sealants that can adhere to a wide range of adherends, especially one-part moisture-curable silicone sealants, are easy to handle, have high heat resistance, and have rubber elasticity, impact resistance and stress relaxation. Excellent in performance and widely used in automobiles, electrical and electronic parts, etc. However, such a one-component moisture-curing silicone sealing agent has a problem that the curing rate is slow, and an improvement in the curing rate is particularly required in a production line that requires high productivity such as an electrical component. In addition, in automobile parts and the like, along with the improvement in performance of various oils including engine oil, the damage of oils to the sealing portion increases, and oil resistance becomes a problem. In order to solve this problem, a curable acrylic sealing agent having improved curing speed and oil resistance has been developed.

  Such curable acrylic sealing agents are conventionally composed of a main agent having a curable functional group (acrylic monomer, reactive acrylic polymer, etc.), an initiator, etc., and curable (meth) acryloyl in the molecule. A sealing agent composition comprising an acrylic rubber having a group, an acrylate polymer and a radical polymerization initiator is known (see Patent Document 1).

  However, acrylic rubber having a curable (meth) acryloyl group lacks flexibility after curing, and in particular, when the amount of the curable functional group introduced is increased in order to further improve the curing rate, the flexibility of the cured product is reduced. Further decrease. For this reason, the sealing agent containing this acrylic rubber has the problem that the adhesiveness in a sealing part and followable | trackability are inferior.

By the way, as a reactive acrylic polymer useful as a main component of a curable acrylic sealing agent, a block comprising a methacrylic polymer block having a curable functional group (active energy ray-curable functional group) and an acrylic polymer block. Copolymers are known (see Patent Document 2). Such a block copolymer separates the curable methacrylic polymer block and the flexible acrylic polymer block, so that the flexibility of the cured product can be increased even if the amount of curable functional groups introduced is increased. It can be expected that it will not be damaged.
However, it is required to satisfy both the curing speed and the flexibility of the cured product at a higher level.

JP 10-152671 A JP 2011-184678 A

  An object of the present invention is to provide a curable sealing agent that is excellent in curing speed and flexibility after curing.

According to the invention, the object is
[1] A (meth) acrylic polymer block (a) having a curable functional group represented by the following general formula (1) (hereinafter referred to as “curable functional group (1)”) (hereinafter simply referred to as “(meta ) Acrylic polymer block (a) ”) and (meth) acrylic polymer block (b) having no curable functional group (hereinafter simply referred to as“ (meth) acrylic polymer block (b) ”). (Meth) acrylic block copolymer (A) (hereinafter simply referred to as “(meth) acrylic block copolymer (A)”) and a polymerization initiator comprising a polymerization initiator Sealing agent;
[2] The curable sealing agent according to the above [1], wherein the polymerization initiator is selected from the group consisting of azo initiators, peroxides, and persulfates; and [3] (meth) acrylic block copolymer This is achieved by providing the curable sealing agent according to the above [1] or [2], wherein the combined body (A) has three or more curable functional groups (1).

（式中、Ｒ¹は水素原子または炭素数１〜２０の炭化水素基を表し、Ｒ²およびＲ³はそれぞれ独立して水素原子または炭素数１〜６の炭化水素基を表し、ＸはＯ、Ｓ、またはＮ（Ｒ⁶）（Ｒ⁶は水素原子または炭素数１〜６の炭化水素基を表す）を表し、ｎは２〜２０の整数を表す）

(In the formula, 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 represents O , S, or N (R ⁶ ) (R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), and n represents an integer of 2 to 20)

  Since the curable sealing agent of the present invention has a high curing rate, the productivity is good, and the cured product is excellent in flexibility. Therefore, the adhesiveness and followability at the sealing portion are high, and an excellent sealing property can be exhibited.

Hereinafter, the present invention will be described in detail.
The curable sealing agent of the present invention contains a (meth) acrylic block copolymer (A). The (meth) acrylic block copolymer (A) includes a (meth) acrylic polymer block (a) having a curable functional group (1). In the (meth) acrylic block copolymer (A), the curable functional group (1) is polymerized and cured by a polymerization initiator. In the present specification, “(meth) acryl” means a generic name of “methacryl” and “acryl”, and “(meth) acryloyl” described later means a generic name of “methacryloyl” and “acryloyl”. “Di (meth) acrylate”, which will be described later, is a general term for “dimethacrylate” and “diacrylate”.

The content of the (meth) acrylic block copolymer (A) in the curable sealing agent of the present invention is preferably 20% by mass or more, and more preferably 40% by mass or more.
The (meth) acrylic polymer block (a) in the (meth) acrylic block copolymer (A) has a curable functional group (1) represented by the following general formula (1).

（式中、Ｒ¹は水素原子または炭素数１〜２０の炭化水素基を表し、Ｒ²およびＲ³はそれぞれ独立して水素原子または炭素数１〜６の炭化水素基を表し、ＸはＯ、Ｓ、またはＮ（Ｒ⁶）（Ｒ⁶は水素原子または炭素数１〜６の炭化水素基を表す）を表し、ｎは２〜２０の整数を表す）

(In the formula, 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 represents O , S, or N (R ⁶ ) (R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), and n represents an integer of 2 to 20)

In the general formula (1), examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a 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, alkyl groups such as n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, n-decyl; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; phenyl group, naphthyl group, etc. Aryl groups; aralkyl groups such as benzyl and phenylethyl groups. Among these, from the viewpoint of curability, a methyl group and an ethyl group are preferable, and a methyl group is most preferable.

In general formula (1), X represents O, S, or N (R ⁶ ) (R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), and is O for ease of polymerization control. Is preferred. When X is N (R ⁶ ), examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an 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 And alkyl groups such as neopentyl group, n-hexyl group, 2-methylpentyl group and 3-methylpentyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group, and phenyl group.

The curable sealing agent of the present invention is applied to a base material, cured and used as a cured product, and then the cured product is easily removed from the base material when it is necessary to disassemble it during re-working or recycling. It is desirable that it can be easily peeled off by, for example, wet pyrolysis. From the viewpoint of having excellent wet heat decomposability after curing, in the general formula (1), R ² and R ³ are preferably hydrocarbon groups having 1 to 6 carbon atoms.

In the general formula (1), examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ² and R ³ include, for example, 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, Alkyl groups such as neopentyl group, n-hexyl group, 2-methylpentyl group and 3-methylpentyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; and aryl groups such as phenyl group It is done. R ² and R ³ are each preferably a hydrocarbon group having 1 to 6 carbon atoms, and a methyl group and an ethyl group are more preferable from the viewpoint of achieving both a curing rate and a reduced viscosity.

In the general formula (1), the integer of 2 to 20 represented by n is preferably 2 to 5 from the viewpoint of fluidity and curing speed of the curable sealing agent.
The content of the curable functional group (1) with respect to all the monomer units forming the (meth) acrylic polymer block (a) is preferably in the range of 0.2 to 100 mol%, and 10 to 90 mol%. The range is more preferable, and the range of 25 to 80 mol% is more preferable.

  The (meth) acrylic polymer block (a) includes a monomer unit formed by polymerizing a monomer containing a (meth) acrylic acid ester. As such a (meth) acrylic acid ester, a monofunctional (meth) acrylic acid ester having one (meth) acryloyl group and a polyfunctional (meth) acrylic acid ester having two or more (meth) acryloyl groups are used. can do.

  Examples of the monofunctional (meth) acrylic acid ester that can form the (meth) acrylic polymer block (a) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, ( (Meth) acrylic acid 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) Dodecyl acrylate, trimethoxysilylpropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ( (Meth) acrylic acid phenyl, (meth) acrylic acid naphthyl, (meth) acrylic acid 2- ( Trimethyl silyloxy) ethyl, and a mono (meth) acrylic acid esters such as (meth) acrylic acid 3- (trimethylsilyloxy) propyl. Among these, methacrylic acid alkyl esters having an alkyl group having 5 or less carbon atoms, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and t-butyl methacrylate are preferable.

Further, as a polyfunctional (meth) acrylic acid ester capable of forming the (meth) acrylic polymer block (a), a bifunctional (meth) acrylic acid ester represented by the following general formula (2) (hereinafter referred to as “di (meta) ) Acrylate (2) ”) is used to carry out living anion polymerization under the conditions described later, thereby producing one (meth) acryloyloxy group (“ CH ₂ ═C (R ⁵ ) in the general formula (2) below ”. (Meth) acryloyloxy group represented by C (O) O ”is selectively polymerized, and R ¹ is R ⁴ , R ² and R ³ are R ^{2 ′} and R ^{3 ′} , and X is O When a (meth) acrylic polymer block (a) having a functional functional group (1) is obtained and the curable sealing agent is cured and used, disassembly during re-working or recycling has occurred. If cured using, for example, a wet pyrolysis method It is preferable because the product and the substrate can be easily separated and separated.

（式中、Ｒ^2'およびＲ^3'はそれぞれ独立して炭素数１〜６の炭化水素基を表し、Ｒ⁴およびＲ⁵はそれぞれ独立して水素原子またはメチル基を表し、ｎは２〜２０の整数を表す）
一般式（２）中、Ｒ^2'およびＲ^3'が表す炭素数１〜６の炭化水素基の例としては上記一般式（１）のＲ²およびＲ³と同様の炭化水素基が挙げられる。

(Wherein R ^{2 ′} and R ^{3 ′} each independently represent a hydrocarbon group having 1 to 6 carbon atoms, R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, and n represents 2 to 2) Represents an integer of 20)
In the general formula (2), examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ^{2 ′} and R ^{3 ′} include the same hydrocarbon groups as R ² and R ^{3 in} the general formula (1). .

From the viewpoint of increasing the selectivity in the polymerization of di (meth) acrylate (2), R ⁴ is preferably a methyl group. Further, from the viewpoint of productivity of the di (meth) acrylate (2), it is preferred that R ⁴ and R ⁵ are the same. From the above viewpoints, it is most preferable that R ⁴ and R ⁵ are both methyl groups.

Specific examples of the di (meth) acrylate (2) include, for example, 1,1-dimethylpropane-1,3-diol di (meth) acrylate, 1,1-dimethylbutane-1,4-diol di (meth) acrylate, 1 , 1-dimethylpentane-1,5-diol di (meth) acrylate, 1,1-dimethylhexane-1,6-diol di (meth) acrylate, 1,1-diethylpropane-1,3-diol di (meth) acrylate, 1,1-diethylbutane-1,4-diol di (meth) acrylate, 1,1-diethylpentane-1,5-diol di (meth) acrylate, 1,1-diethylhexane-1,6-diol di (meth) acrylate From the viewpoint of increasing the selectivity in polymerization of di (meth) acrylate (2), 1,1-di Tylpropane-1,3-diol dimethacrylate, 1,1-dimethylbutane-1,4-diol dimethacrylate, 1,1-dimethylpentane-1,5-diol dimethacrylate, 1,1-dimethylhexane-1,6 -Diol dimethacrylate, 1,1-diethylpropane-1,3-diol dimethacrylate, 1,1-diethylbutane-1,4-diol dimethacrylate, 1,1-diethylpentane-1,5-diol dimethacrylate, And 1,1-diethylhexane-1,6-diol dimethacrylate, 1,1-dimethylpropane-1,3-diol dimethacrylate, 1,1-dimethylbutane-1,4-diol dimethacrylate, 1-dimethylpentane-1,5-diol dimethacrylate, and , 1-dimethyl-hexane-1,6-diol dimethacrylate are more preferred.
These (meth) acrylic acid esters may be used alone or in combination of two or more.

  The content of the monomer unit formed from the (meth) acrylic acid ester in the (meth) acrylic polymer block (a) is the total monomer forming the (meth) acrylic polymer block (a). The range of 90-100 mol% is preferable with respect to the unit, the range of 95-100 mol% is more preferable, and 100 mol% may be sufficient. In addition, when the (meth) acrylic polymer block (a) includes a monomer unit formed from di (meth) acrylate (2), a single unit formed from di (meth) acrylate (2) is used. The content of the monomer unit is preferably in the range of 0.2 to 100 mol%, more preferably in the range of 10 to 90 mol%, based on all monomer units forming the (meth) acrylic polymer block (a). More preferably, the range of 25 to 80 mol% is more preferable. Furthermore, the sum of the content of monomer units formed from methyl methacrylate and the content of monomer units formed from di (meth) acrylate (2) is formed from (meth) acrylic acid esters. The range of 80-100 mol% is preferable with respect to all monomer units, the range of 90-100 mol% is more preferable, the range of 95-100 mol% is more preferable, and 100 mol% may be sufficient.

  The (meth) acrylic polymer block (a) may have a monomer unit formed from a monomer other than (meth) acrylic acid ester. Examples of the other monomer include α-alkoxy acrylate esters such as methyl α-methoxyacrylate and methyl α-ethoxyacrylate; crotonic acid esters such as methyl crotonate and ethyl crotonate; 3-methoxyacrylic acid. 3-alkoxyacrylic esters such as esters; N-isopropylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and other acrylamides; N-isopropylmethacrylamide, Nt-butyl Methacrylamide, such as methacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide; methyl 2-phenylacrylate, ethyl 2-phenylacrylate, n-butyl 2-bromoacrylate, 2-bromomethylacrylate Methyl acrylic acid, 2-bromomethyl acrylate, methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone, ethyl isopropenyl ketone. These other monomers may be used alone or in combination of two or more.

  The content of the monomer units formed from the other monomers in the (meth) acrylic polymer block (a) is the total monomer forming the (meth) acrylic polymer block (a). 10 mol% or less is preferable with respect to the unit, and 5 mol% or less is more preferable.

  The number average molecular weight (Mn) per (meth) acrylic polymer block (a) is not particularly limited, but the handleability, fluidity, mechanical properties, etc. of the resulting (meth) acrylic block copolymer are not limited. From the viewpoint, it is preferably in the range of 500 to 1,000,000, and more preferably in the range of 1,000 to 300,000. In addition, in this specification, Mn means the number average molecular weight of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.

The (meth) acrylic block copolymer (A) includes a (meth) acrylic polymer block (b) having no curable functional group.
In the present specification, the curable functional group means a functional group exhibiting polymerizability. Examples of the curable functional group include (meth) acryloyl group, (meth) acryloyloxy group, vinyl group, allyl group, vinyloxy group, 1,3-dienyl group, styryl group and other ethylenic double bonds (particularly general formula A functional group having CH ₂ ═CHR— (wherein R is an alkyl group or a hydrogen atom); an epoxy group, an oxetanyl group, a thiol group, a maleimide group, and the like.

  The (meth) acrylic polymer block (b) is composed of a monomer unit formed by polymerizing a monomer containing a (meth) acrylic acid ester and does not have the above-described curable functional group. It is a polymer block.

  Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, T-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, dodecyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, ( N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (meta ) 2- (Trimethylsilyloxy) ethyl acrylate, (meth) acrylic acid - include mono (meth) acrylic acid esters such as (trimethylsilyl) propyl. Among these, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, alkyl acrylate having an alkyl group with 4 or more carbon atoms such as 2-decyl acrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate A methacrylic acid alkyl ester having an alkyl group having 6 or more carbon atoms such as is preferred. In addition, these (meth) acrylic acid ester may use only 1 type, or may use 2 or more types.

  The content of the monomer unit formed by the (meth) acrylic ester in the (meth) acrylic polymer block (b) is the total monomer forming the (meth) acrylic polymer block (b). It is preferably 90 mol% or more, more preferably 95 mol% or more, and may be 100 mol% with respect to the unit.

  The (meth) acrylic polymer block (b) may have a monomer unit formed by a monomer other than the (meth) acrylic acid ester. Examples of the other monomers include α-alkoxy acrylates such as α-methyl acrylate and methyl α-ethoxy acrylate; crotonates such as methyl crotonate and ethyl crotonate; 3-methoxy acrylate. 3-alkoxyacrylic acid esters such as N-isopropylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and the like; N-isopropylmethacrylamide, Nt-butylmethacryl Examples thereof include amides such as amide, N, N-dimethylmethacrylamide and N, N-diethylmethacrylamide; methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone and ethyl isopropenyl ketone. These other monomers may be used alone or in combination of two or more.

  The content of monomer units formed by the other monomers in the (meth) acrylic polymer block (b) is the total amount of the monomer units forming the (meth) acrylic polymer block (b). 10 mol% or less is preferable with respect to the monomer unit, and 5 mol% or less is more preferable.

  Although there is no restriction | limiting in particular in Mn per (meth) acrylic-type polymer block (b), From the point of the handleability of the (meth) acrylic-type block copolymer of this invention, fluidity | liquidity, a mechanical characteristic, etc., 3 It is preferably in the range of 2,000 to 2,000,000, and more preferably in the range of 5,000 to 1,000,000.

  The (meth) acrylic block copolymer (A) is a block in which at least one (meth) acrylic polymer block (a) and at least one (meth) acrylic polymer block (b) are bonded to each other. Although it is a copolymer and there is no restriction | limiting in particular in the number and coupling | bonding order of each polymer block, (meth) acrylic-type polymer block (a) is (meth) acrylic-type block copolymer (A from a viewpoint of a cure rate. ) At least one terminal is preferable, and from the viewpoint of ease of production of the (meth) acrylic block copolymer, a linear polymer is more preferable, and one (meth) acrylic is preferable. Both ends of a diblock copolymer in which a polymer block (a) and one (meth) acrylic polymer block (b) are bonded and one (meth) acrylic polymer block (b) (Meth) acrylic polymer block (a) tri-block copolymer each one is attached respectively are more preferred.

  Ratio of mass of (meth) acrylic polymer block (a) and mass of (meth) acrylic polymer block (b) constituting (meth) acrylic block copolymer (A) ((meth) acrylic) The polymer block (a) :( meth) acrylic polymer block (b)) is not particularly limited, but is preferably 90:10 to 5:95. The ratio of the mass of the (meth) acrylic polymer block (a) to the total mass of the (meth) acrylic polymer block (a) and the (meth) acrylic polymer block (b) is 5% or more. When it is 90% or less, the viscoelasticity is improved, which is preferable.

  Although there is no restriction | limiting in particular in Mn of a (meth) acrylic block copolymer (A), From points, such as the handleability of a (meth) acrylic block copolymer (A), fluidity | liquidity, a mechanical characteristic, 4,000. It is preferably ˜3,000,000, more preferably 7,000 to 2,000,000. The molecular weight distribution (Mw / Mn) of the (meth) acrylic block copolymer (A) is preferably 1.5 or less.

  The content of the curable functional group (1) in the (meth) acrylic block copolymer (A) is 0. 0 with respect to all monomer units forming the (meth) acrylic block copolymer (A). The range is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and still more preferably 3 to 10 mol%.

  The number of curable functional groups (1) in the (meth) acrylic block copolymer (A) is preferably 3 or more, more preferably 4 or more, from the viewpoint of curing speed. More preferably, it is one or more.

  The block copolymer (A) can be obtained by forming the (meth) acrylic polymer block (a) and the (meth) acrylic polymer block (b) in a desired order. The production method of the block copolymer (A) in the present invention is not particularly limited, but an anionic polymerization method or a radical polymerization method is preferable, an anionic polymerization method is more preferable because of easy control of the polymerization reaction, and a living anionic polymerization method is particularly preferable. Further preferred. The monomer used for the production of the block copolymer (A) is preferably previously dried in an inert gas atmosphere from the viewpoint of allowing the polymerization to proceed smoothly. In the drying treatment, a dehydrating agent or a drying agent such as calcium hydride, molecular sieves, activated alumina or the like is preferably used.

  Living radical polymerization methods include a polymerization method using a chain transfer agent such as polysulfide, a polymerization method using a cobalt porphyrin complex, a polymerization method using a nitroxide (see International Publication No. 2004/014926), and a high cycle such as an organic tellurium compound. Polymerization method using a hetero element compound (see Japanese Patent No. 3839829), reversible addition / desorption chain transfer polymerization method (RAFT) (see Japanese Patent No. 3639859), atom transfer radical polymerization method (ATRP) (Japanese Patent No. 3040172) Gazette, International Publication No. 2004/013192). Among these living radical polymerization methods, an atom transfer radical polymerization method is preferred, and a metal complex having an organic halide or a sulfonyl halide compound as an initiator and at least one selected from Fe, Ru, Ni, and Cu as a central metal is used. An atom transfer radical polymerization method using a catalyst is more preferable.

  Living anionic polymerization methods include a method of living polymerization using an organic rare earth metal complex as a polymerization initiator (see JP-A-06-93060), an alkali metal or alkaline earth metal salt using an organic alkali metal compound as a polymerization initiator, and the like. A living anion polymerization in the presence of a mineral acid salt (see JP 05-507737 A), and a living anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound (Japanese Patent Laid-Open No. Hei 5). 11-335432 and International Publication No. 2013/141105). Among these living anionic polymerization methods, from the viewpoint of production efficiency of the (meth) acrylic block copolymer (A), there is a method of living anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organic aluminum compound. Preferably, a method of living anion polymerization using an organolithium compound as a polymerization initiator in the presence of an organoaluminum compound and a Lewis base is more preferred.

As said organoaluminum compound, the organoaluminum compound shown by the following general formula (A-1) or (A-2) is mentioned.
AlR ⁷ (R ⁸ ) (R ⁹ ) (A-1)
Wherein R ⁷ represents a monovalent saturated hydrocarbon group, monovalent aromatic hydrocarbon group, alkoxy group, aryloxy group or N, N-disubstituted amino group, and R ⁸ and R ⁹ are each independently Or R ⁸ and R ⁹ are bonded to each other to form an aryleneoxy group)
AlR ¹⁰ (R ¹¹ ) (R ¹² ) (A-2)
(Wherein R ¹⁰ represents an aryloxy group, R ¹¹ and R ¹² each independently represent a monovalent saturated hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group, or an N, N-disubstituted amino group. Represents a group)

In the general formulas (A-1) and (A-2), examples of the aryloxy group that R ⁷ , R ⁸ , R ^9, and R ¹⁰ each independently represent include a phenoxy group, a 2-methylphenoxy group, and 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-methyl Phenoxy 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, Examples include 7-methoxy-2-naphthoxy group.

In the above general formula (A-1), examples of the aryleneoxy group formed by bonding R ⁸ and R ⁹ to each other include 2,2′-biphenol, 2,2′-methylenebisphenol, 2,2 ′. -Methylenebis (4-methyl-6-tert-butylphenol), (R)-(+)-1,1'-bi-2-naphthol, (S)-(-)-1,1'-bi-2- The functional group which remove | excluded the hydrogen atom of these two phenolic hydroxyl groups in the compound which has two phenolic hydroxyl groups, such as a naphthol, is mentioned.

  In addition, one or more hydrogen atoms contained in the above aryloxy group and aryleneoxy group may be substituted with a substituent. Examples of the substituent include a methoxy group, an ethoxy group, an isopropoxy group, Examples thereof include alkoxy groups such as t-butoxy group; halogen atoms such as chlorine and bromine.

In the general formulas (A-1) and (A-2), examples of the monovalent saturated hydrocarbon group represented by R ⁷ , R ^11, and R ¹² independently include a methyl group, an ethyl group, and n-propyl. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 2-methylbutyl group, 3-methylbutyl group, n-octyl group, 2-ethylhexyl group and other alkyl groups; cyclohexyl group, etc. The monovalent aromatic hydrocarbon group includes, for example, an aryl group such as a phenyl group; the aralkyl group such as a benzyl group; and the alkoxy group includes, for example, a methoxy group and an ethoxy group. , Isopropoxy group, t-butoxy group and the like. Examples of the N, N-disubstituted amino group include dimethylamino group, diethylamino group, diisopropylamino group, and the like. Dialkylamino groups such as bis (trimethylsilyl) amino group and the like. One or more hydrogen atoms contained in the above-mentioned monovalent saturated hydrocarbon group, monovalent aromatic hydrocarbon group, alkoxy group and N, N-disubstituted amino group may be substituted with a substituent. Examples of the substituent include alkoxy groups such as methoxy group, ethoxy group, isopropoxy group and t-butoxy group; halogen atoms such as chlorine and bromine.

  Examples of the organoaluminum compound (A-1) include ethylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, ethylbis (2,6-di-t-butylphenoxy) aluminum, ethyl [2 , 2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, isobutylbis (2,6-di-tert-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′-methyl Bis (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-tert-butylphenoxy)] aluminum, ethoxybis (2,6-di-tert-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-tert-butylphenoxy)] aluminum, t-butoxybis (2,6-di-tert-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 and the like. Among them, from the viewpoints of polymerization initiation efficiency, living property of polymerization terminal anion, availability and handling, etc., 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 and the like are preferable.

  Examples of the organoaluminum compound (A-2) include diethyl (2,6-di-t-butyl-4-methylphenoxy) aluminum, diethyl (2,6-di-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, di-n-octyl (2,6-di-t-butylphenoxy) aluminum and the like. These organoaluminum compounds may be used alone or in combination of two or more.

  The amount of the organoaluminum compound used can be appropriately selected in accordance with the type of solvent, other various polymerization conditions, etc., but is generally 1.0 to 10 with respect to 1 mol of the organic lithium compound from the viewpoint of the polymerization rate. It is preferably used in the range of 0.0 mol, more preferably in the range of 1.1 to 5.0 mol, and still more preferably in the range of 1.2 to 4.0 mol. If the amount of the organoaluminum compound used exceeds 10.0 mol with respect to 1 mol of the organolithium compound, it tends to be disadvantageous in terms of economy, and if it is less than 1.0 mol, the polymerization initiation efficiency tends to decrease.

  The Lewis base includes an ether bond and / or a tertiary amine structure in the molecule (—RN (R ′ —) — R ″ —: R, R ′ and R ″ represent a divalent organic group). The compound which has is mentioned.

  Examples of the compound used as the Lewis base and having an ether bond in the molecule include ether. The ether is 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 high polymerization initiation efficiency and living property of the polymerization terminal anion. Is preferred. 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 one or more ether bonds in the molecule include acyclic monoethers such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, and anisole; 1,2-dimethoxyethane, 1,2-diethoxy Ethane, 1,2-diisopropoxyethane, 1,2-dibutoxyethane, 1,2-diphenoxyethane, 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, , 3-diphenoxypropane, 1,4-dimethoxybutane, 1,4-diethoxybutane, , 4-diisopropoxybutane, 1,4-dibutoxybutane, 1,4-diphenoxybutane and the like acyclic diethers; 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, tetrapropylene glycol dimethyl ether Tetrabutylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetrapropylene glycol diethyl ether, acyclic polyethers such as tetramethylammonium butylene glycol diethyl ether. Among these, from the viewpoints of suppressing side reactions and availability, acyclic ether having 1 to 2 ether bonds in the molecule is preferable, and diethyl ether or 1,2-dimethoxyethane is more preferable.

  The compound having a tertiary amine structure in the molecule used as the Lewis base includes tertiary polyamine. A tertiary polyamine means a compound having two or more tertiary amine structures in the molecule. Examples of the tertiary polyamine include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyl. Linear polyamines such as diethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetraamine, 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-hexamethyl-1,4,7,10,13,16 -Non-aromatic heterocyclic compounds such as hexaazacyclooctadecane; aromatic heterocyclic compounds such as 2,2'-bipyridyl and 2,2 ': 6', 2 "-terpyridine .

  A compound having one or more ether bonds and one or more tertiary amine structures in the molecule may be used as the Lewis base. Examples of such a compound include tris [2- (2-methoxyethoxy) ethyl] amine.

These Lewis bases may be used alone or in combination of two or more.
The amount of the Lewis base used is preferably in the range of 0.3 to 5.0 mol with respect to 1 mol of the organic lithium compound from the viewpoints of polymerization initiation efficiency, stability of the polymerization terminal anion, and the like. The range of 3.0 mol is more preferable, and the range of 1.0 to 2.0 mol is more preferable. When the amount of the Lewis base used exceeds 5.0 mol with respect to 1 mol of the organolithium compound, it tends to be disadvantageous in terms of economy, and when it is less than 0.3 mol, the polymerization initiation efficiency tends to decrease.

  In addition, the amount of Lewis base used is preferably in the range of 0.2 to 1.2 mol, and in the range of 0.3 to 1.0 mol, with respect to 1 mol of the tertiary organoaluminum compound. Is more preferable.

  Examples of the organolithium compound include t-butyllithium, 1,1-dimethylpropyllithium, 1,1-diphenylhexyllithium, 1,1-diphenyl-3-methylpentyllithium, ethyl α-lithioisobutyrate, butyl α-lithioisobutyrate, methyl α-lithioisobutyrate, isopropyl lithium, sec-butyl lithium, 1-methylbutyl lithium, 2-ethylpropyl lithium, 1-methylpentyl lithium, cyclohexyl lithium, diphenylmethyl lithium, α- Examples include methyl benzyl lithium, methyl lithium, n-propyl lithium, n-butyl lithium, n-pentyl lithium and the like. Among them, from the viewpoint of availability and anion polymerization initiating ability, secondary grades such as isopropyl lithium, sec-butyl lithium, 1-methylbutyl lithium, 1-methylpentyl lithium, cyclohexyl lithium, diphenylmethyl lithium, α-methylbenzyl lithium, etc. C3-C40 organolithium compounds having a chemical structure with a carbon atom as an anion center are preferred, and sec-butyllithium is particularly preferred. These organolithium compounds may be used alone or in combination of two or more.

  The living anionic polymerization is preferably performed in the presence of an organic solvent from the viewpoint of temperature control during polymerization and homogenization in the system. Organic solvents include hydrocarbons such as toluene, xylene, cyclohexane, and methylcyclohexane; halogenated hydrocarbons such as chloroform, methylene chloride, and carbon tetrachloride from the viewpoints of safety and ease of recovery and reuse after polymerization. An ester such as dimethyl phthalate is preferred. These organic solvents may be used alone or in combination of two or more. In addition, it is preferable to deaerate the organic solvent in advance in the presence of an inert gas while performing a drying treatment from the viewpoint of smoothly proceeding anionic polymerization.

  In the living anionic polymerization, other additives may be present in the anionic polymerization reaction system as necessary. Examples of the other additives include inorganic salts such as lithium chloride; metal alkoxides such as lithium methoxyethoxy ethoxide and potassium t-butoxide; tetraethylammonium chloride and tetraethylphosphonium bromide.

  The living anionic polymerization is preferably performed at -30 to 25 ° C. When it is lower than −30 ° C., the polymerization rate is lowered and the productivity tends to be lowered. On the other hand, when it is higher than 25 ° C., it tends to be difficult to polymerize the curable functional group (1) with good living property.

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

  In the above living anionic polymerization, as a method of adding an organolithium compound, organoaluminum compound, Lewis base and monomer to the reaction system, the Lewis base is brought into contact with the organoaluminum compound before contacting with the organolithium compound. It is preferable to add. The organoaluminum compound may be added to the reaction system before the monomer or simultaneously. When the organoaluminum compound is added to the reaction system simultaneously with the monomer, the organoaluminum compound may be added after separately mixing with the monomer.

  The living anionic polymerization can be stopped by adding a polymerization terminator such as methanol; acetic acid or a methanol solution of hydrochloric acid; or a protic compound such as an aqueous solution of acetic acid or hydrochloric acid to the reaction system. The amount of the polymerization terminator used is usually preferably in the range of 1 to 100 mol with respect to 1 mol of the organic lithium compound used.

  As a method for separating and obtaining the (meth) acrylic block copolymer (A) from the reaction mixture after stopping the living anion polymerization, a known method can be adopted. For example, a method in which the reaction mixture is poured into a poor solvent for the (meth) acrylic block copolymer to precipitate the (meth) acrylic block copolymer, and the organic solvent is distilled off from the reaction mixture (meth) acrylic. The method etc. which acquire a system block copolymer are mentioned.

  If the metal component derived from the organolithium compound and the tertiary organoaluminum compound remains in the (meth) acrylic block copolymer (A) obtained separately, the (meth) acrylic block copolymer This may cause deterioration of physical properties and poor transparency. Therefore, it is preferable to remove the metal component derived from the organolithium compound and the tertiary organoaluminum compound after the anionic polymerization is stopped. As a method for removing the metal component, the (meth) acrylic block copolymer may be subjected to a washing treatment using an acidic aqueous solution, an adsorption treatment using an adsorbent such as an ion exchange resin, celite, or activated carbon. It is valid. Here, as 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. can be used, for example.

  As a method of introducing the curable functional group (1) in the production of the (meth) acrylic block copolymer (A), a monomer containing the di (meth) acrylate (2) described above is polymerized. In addition to the method of forming the (meth) acrylic polymer block (a), a polymer block containing a partial structure (hereinafter referred to as “precursor structure”) serving as a precursor of the curable functional group (1). A method of converting the precursor structure into the curable functional group (1) after the formation is also mentioned. A polymer block containing a precursor structure can be obtained by polymerizing a monomer containing a polymerizable functional group and a compound containing a precursor structure. Examples of the polymerizable functional group include a styryl group, a 1,3-dienyl group, a vinyloxy group, a (meth) acryloyl group, and a (meth) acryloyl group is preferable. The precursor structure includes hydroxyl groups protected by hydroxyl groups and protecting groups (silyloxy groups, acyloxy groups, alkoxy groups, etc.), amino groups protected by isocyanate groups, amino groups and protecting groups, and protected by thiol groups and protecting groups. The thiol group etc. which were made are mentioned.

  A polymer block containing a hydroxyl group as a precursor structure is reacted with a compound having a curable functional group (1) and a partial structure (carboxylic acid, ester, carbonyl halide, etc.) capable of reacting with a hydroxyl group, and (meth) acrylic. A polymer block (a) can be formed. In addition, a polymer block containing a hydroxyl group protected by a protecting group as a precursor structure can form a (meth) acrylic polymer block (a) after removing the protecting group to form a hydroxyl group.

  The polymer block containing an isocyanate group as a precursor structure is reacted with a compound having a curable functional group (1) and a partial structure capable of reacting with an isocyanate group (such as a hydroxyl group) to form a (meth) acrylic polymer block ( a) can be formed.

  A polymer block containing an amino group as a precursor structure is a curable functional group (1) and a partial structure capable of reacting with an amino group (carboxylic acid, carboxylic anhydride, ester, carbonyl halide, aldehyde group, isocyanate group, etc.) The polymer block (a) can be formed by reacting with a compound having the following. A polymer block containing an amino group protected by a protective group as a precursor structure can form a polymer block (a) in the same manner after removing the protective group to form an amino group.

  The polymer block containing a thiol group as a precursor structure has a curable functional group (1) and a partial structure capable of reacting with the thiol group (carboxylic acid, carboxylic anhydride, ester, carbonyl halide, isocyanate group, carbon-carbon dioxygen). The polymer block (a) can be formed by reacting with a compound having a heavy bond or the like. In addition, a polymer block containing a thiol group protected by a protecting group as a precursor structure can form a polymer block (a) in the same manner after removing the protecting group to form a thiol group.

  In the production of the (meth) acrylic block copolymer (A), as a method of forming the (meth) acrylic polymer block (a), from the viewpoint that the curable functional group (1) can be easily introduced directly, A method of polymerizing a monomer containing di (meth) acrylate (2), typically a method of living anion polymerization, is preferred.

  The curable sealing agent of the present invention contains a polymerization initiator. As a polymerization initiator, light that initiates polymerization of the main agent ((meth) acrylic block copolymer (A) and a reactive diluent described later, which is an optional component) by irradiation with active energy rays such as UV and electron beams. Examples thereof include a polymerization initiator and a thermal polymerization initiator that initiates polymerization of the main agent by heat.

Examples of the photopolymerization initiator that can be contained in the curable sealing agent of the present invention include acetophenones (for example, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy- 2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, etc.), benzophenones (for example, benzophenone, benzoylbenzoic acid, hydroxybenzophenone) , 3,3′-dimethyl-4-methoxybenzophenone, acrylated benzophenone, etc.), Michler ketones (eg, Michler ketone, etc.) and benzoins (eg, benzoin, benzoin methyl ether, benzoin isopropyl ether, etc.); Sulfur compounds such as methyl thiuram monosulfide and thioxanthones (eg thioxanthone, 2-chlorothioxanthone etc.); acylphosphine oxides (eg 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4 , 6-trimethylbenzoyl) -phenylphosphine oxide and the like; titanocenes (for example, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- ( 1H-pyrrol-1-yl) -phenyl) titanium, etc.). Among these, acetophenones and benzophenones are preferable. These photopolymerization initiators may be used alone or in combination of two or more.

  When the curable sealing agent of the present invention contains a photopolymerization initiator, the content of the curable sealing agent is the main component ((meth) acrylic block copolymer (A) and optional components contained in the curable sealing agent of the present invention. 0.01 to 10 parts by mass, and more preferably 0.05 to 8 parts by mass with respect to 100 parts by mass of a reactive diluent described later. If it is 0.01 part by mass or more, the curability of the curable sealing agent will be good, and if it is 10 parts by mass or less, the resulting cured product tends to have good heat resistance. In addition, when using together 2 or more types of photoinitiators, the content means a total amount.

  Further, the curable sealing agent of the present invention may contain a sensitizer in addition to the photopolymerization initiator. Examples of the sensitizer include n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiouric acid, triethylamine, diethylaminoethyl methacrylate and the like. Among these, diethylaminoethyl methacrylate and triethylamine are preferable.

  When a photopolymerization initiator and a sensitizer are mixed and used, the mass ratio of the photopolymerization initiator and the sensitizer is preferably in the range of 10:90 to 90:10, and 20:80 to 80: A range of 20 is more preferred.

  When the curable sealing agent of the present invention contains a photopolymerization initiator, it can be cured by irradiation with active energy rays. As such active energy rays, light rays, electromagnetic waves, particle rays and combinations thereof can be used, but ultraviolet rays or electron beams are preferable, and ultraviolet rays are more preferable from the viewpoints of curing speed, availability of an irradiation apparatus, price, and the like.

  The active energy ray can be irradiated using a known apparatus. In the case of an electron beam (EB), an acceleration voltage of 0.1 to 10 MeV and an irradiation dose of 1 to 500 kGy are appropriate.

For the ultraviolet irradiation, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an LED, or the like that emits light having a wavelength range of 150 to 450 nm can be used. Integrated light quantity of active energy rays, usually in the range of 10~20000mJ / cm ^2, the range of 30~5000mJ / cm ² is preferred. If it is less than 10 mJ / cm ² , the curability of the curable sealing agent tends to be insufficient, and if it exceeds 20000 mJ / cm ² , the curable sealing agent may be deteriorated.

  The relative humidity when irradiating active energy rays to the curable sealing agent of the present invention is preferably 30% or less, and preferably 10% or less from the viewpoint of suppressing decomposition of the curable sealing agent. More preferred.

  The curable sealing agent of the present invention can be further cured by heating as necessary during or after irradiation with active energy rays to promote curing. The heating temperature is preferably in the range of 40 to 130 ° C, more preferably in the range of 50 to 100 ° C.

The thermal polymerization initiator that can be contained in the curable sealing agent of the present invention is not particularly limited, but an azo initiator [for example, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (VAZO33, etc.), 2,2′-azobis (2-amidinopropane) dihydrochloride (manufactured by DuPont Chemical, VAZO50, etc.), 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by DuPont Chemical, VAZO52, etc.), 2, 2'-azobis (isobutyronitrile) (DuPont Chemical, VAZO64, etc.), 2,2'-azobis-2-methylbutyronitrile (DuPont Chemical, VAZO67, etc.), 1,1-azobis (1-cyclohexane) (Carbonitrile) (manufactured by DuPont Chemical, AZO88, etc.), 2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (methylisobutyrate) (manufactured by Wako Pure Chemical Industries, Ltd., V-601, etc.)], peroxides, etc. Benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate (manufactured by Akzo Nobel, Perkadox 16S, etc.), di (2- Ethylhexyl) peroxydicarbonate, t-butylperoxypivalate (manufactured by Elf Atochem, Lupersol 11 and the like), t-butylperoxy-2-ethylhexanoate (manufactured by Akzo Nobel, Trigonox 21-C50 and the like), Cumene hydroperoxide, dicumyl peroxide Etc.], persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), pinacol (tetraphenyl 1,1,2,2-ethanediol, etc.) and the like, and azo initiators, peroxides, and the like Persulfate is preferred.
These thermal polymerization initiators may be used alone or in combination of two or more.

  Further, the curable sealing agent of the present invention may further contain a reducing agent in addition to the thermal polymerization initiator. By containing a reducing agent, the amount of the thermal polymerization initiator used can be reduced, which is preferable. As a preferable combination of the thermal polymerization initiator and the reducing agent, a combination of the persulfate initiator and a reducing agent such as sodium metabisulfite and sodium bisulfite; the peroxide initiator (benzoyl peroxide, etc.) and Combinations with tertiary amines (such as dimethylaniline) and combinations of organic hydroperoxides (such as dicumyl peroxide) and organometallic compounds (such as cobalt naphthate) can be mentioned.

  When the curable sealing agent of the present invention contains a thermal polymerization initiator, the content of the curable sealing agent is the main component ((meth) acrylic block copolymer (A) and optional components contained in the curable sealing agent of the present invention. When the total amount of a certain reactive diluent described later is 100 parts by mass, a range of about 0.01 to 5 parts by mass is preferable, and a range of 0.025 to 2 parts by mass is more preferable. In addition, when using together 2 or more types of thermal-polymerization initiators, the content means a total amount.

  When the curable sealing agent of the present invention contains a thermal polymerization initiator, it can be cured by heating. The heating temperature is preferably in the range of 50 to 250 ° C, more preferably in the range of 70 to 200 ° C. The heating time varies depending on the thermal polymerization initiator, reactive diluent, reaction temperature and the like used, but is usually in the range of 1 minute to 10 hours.

  The curable sealing agent of the present invention may contain a reactive diluent exhibiting polymerizability other than the (meth) acrylic block copolymer (A). Examples of reactive diluents include styrene such as styrene, indene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert-butoxystyrene, p-chloromethylstyrene, p-acetoxystyrene, and divinylbenzene. Derivatives; Fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid n -Propyl, (meth) isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, ( Hexyl (meth) acrylate, heptyl (meth) acrylate , Octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylic acid Undecyl, dodecyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylic acid Bornyl, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, 2- (meth) acrylic acid 2- Hydroxyethyl, 2-hydroxypro (meth) acrylic acid , 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, (meth) Phenoxyethyl acrylate, (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-dimethylo Chill, 4- (meth) acryloylmorpholine, trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di Acrylate, tetraethylene glycol di (meth) acrylate, tricyclodecanediyldimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bis Phenol A diglycidyl ether end (meth) acrylic acid adduct, pentaerythritol tetra (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) ) Acrylate, tricyclodecane dimethanol di (meth) acrylate, di (meth) acrylate of diol that is an adduct of ethylene oxide or propylene oxide of bisphenol A, an adduct of ethylene oxide or propylene oxide of hydrogenated bisphenol A Di (meth) acrylate of diol, epoxy (meth) acrylate obtained by adding (meth) acrylate to diglycidyl ether of bisphenol A, and cyclohexanedimethanol di (meth) (Meth) acrylic acid derivatives such as acrylate; epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolac type epoxy acrylate resin, cresol novolac type epoxy acrylate resin; COOH group-modified epoxy acrylate type resin; polyol (polytetramethylene) Glycol, ethylene glycol and adipic acid polyester diol, ε-caprolactone-modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanate (tolylene diene) Isocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, Urethane resins obtained from hexamethylene diisocyanate, xylylene diisocyanate, etc.) containing hydroxyl group-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc.} Urethane acrylate resin obtained by reacting with the above; resin having (meth) acrylic group introduced through an ester bond to the above polyol; polyester (meth) acrylate resin; epoxidized soybean oil, epoxy benzyl stearate, etc. An epoxy compound etc. are mentioned. These reactive diluents may be used alone or in combination of two or more.

  In the case where a reactive diluent is contained in the curable sealing agent of the present invention, the content thereof is from the viewpoint of increasing the fluidity of the curable sealing agent and the mechanical strength of the cured product obtained from the curable sealing agent. 10-90 mass% is preferable, and 20-80 mass% is more preferable. In addition, when using together 2 or more types of reactive diluents, the content means a total amount.

  The curable sealing agent of the present invention has an active energy ray-curable group such as a plasticizer, a tackifier, a softener, a filler, a stabilizer, a pigment, and a dye within a range that does not significantly inhibit the curability. Various additives may be included.

  The purpose of including the plasticizer in the curable sealing agent of the present invention is, for example, adjustment of the viscosity of the curable sealing agent and adjustment of the mechanical strength of a cured product obtained by curing the curable sealing agent. Examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; non-aromatics such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and isodecyl succinate. Dibasic acid esters; Aliphatic esters such as butyl oleate and methyl acetylricinoleate; Esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol esters; Tricresyl phosphate, tributyl phosphate, and the like Trimellitic acid ester; Polybutadiene, butadiene-acrylonitrile copolymer, diene (co) polymer such as polychloroprene; Polyisobutylene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls; process oils; polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the hydroxyl groups of these polyether polyols Polyethers such as derivatives converted to groups, ether groups, etc .; 2 basic acids such as sebacic acid, adipic acid, azelaic acid, phthalic acid, and 2 such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol Polyester obtained from a monohydric alcohol; and the like. The (co) polymer is a general term for a homopolymer and a copolymer. These plasticizers may be used alone or in combination of two or more.

  When the plasticizer is contained in the curable sealing agent of the present invention, the content is preferably 5 to 150 parts by mass, and 10 to 120 parts by mass with respect to 100 parts by mass of the (meth) acrylic block copolymer (A). Part is more preferable, and 20-100 mass parts is further more preferable. When the amount is 5 parts by mass or more, effects such as physical property adjustment and property adjustment become remarkable, and when the amount is 150 parts by mass or less, a cured product obtained by curing the curable sealing agent tends to have excellent mechanical strength. In addition, when using together 2 or more types of plasticizers, the content means a total amount.

  The molecular weight or Mn (number average molecular weight) of these plasticizers is preferably 400 to 15,000, more preferably 800 to 10,000, and more preferably 1,000 to 8,000. Such a plasticizer may or may not have a functional group other than the active energy ray-curable group (for example, a hydroxyl group, a carboxyl group, a halogen group, etc.). When the molecular weight or Mn of the plasticizer is 400 or more, the plasticizer does not flow out from the cured product of the curable sealing agent with time, and the initial physical properties can be maintained for a long time. Further, when the plasticizer has a molecular weight or Mn of 15000 or less, the curable sealing agent tends to be easy to handle.

  The purpose of including the tackifier in the curable sealing agent of the present invention is to impart tackiness to a cured product obtained from the curable sealing agent, for example. Examples of the tackifier include coumarone / indene resin, phenol resin, pt-butylphenol / acetylene resin, phenol / formaldehyde resin, xylene / formaldehyde resin, aromatic hydrocarbon resin, aliphatic hydrocarbon resin (terpene resin, etc.) , Styrene resins (polystyrene, poly-α-methylstyrene, etc.), polyhydric alcohol esters of rosin, hydrogenated rosin, hydrogenated wood rosin, esters of hydrogenated rosin and monoalcohol or polyhydric alcohol, terpine tackifying resin And the like. Among these, aliphatic hydrocarbon resins (terpene resins and the like), polyhydric alcohol esters of rosin, hydrogenated rosin, hydrogenated wood rosin, esters of hydrogenated rosin and monoalcohol or polyhydric alcohol are preferable.

  The curable sealing agent of the present invention can be prepared as a two-component type comprising components A and B containing a reducing agent, except for the reducing agent. It can also be prepared as a liquid form.

  The curable sealant of the present invention is useful as an elastic sealant, particularly a sealant for construction, a sealant for siding boards, and a sealant for glazing, and can be used as a sealant for buildings, ships, automobiles, roads and the like. . Furthermore, it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, and resin moldings alone or with the help of a primer, so glass sealing materials, various gaskets, medical caps and sealing materials It can be suitably used as a sealing material for food, a sealing material for automobile interior and exterior, a civil engineering / waterproof sheet, an adhesive tape, and the like.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to this Example.
In the following Examples and Comparative Examples, the raw materials were dried and purified by a conventional method and degassed with nitrogen, and the transfer and supply were performed under a nitrogen atmosphere.

[Monomer consumption rate]
The consumption rate of each monomer after polymerization was calculated by the following method. That is, 0.5 ml of a polymerization reaction solution collected from the polymerization system was put into 0.5 ml of methanol to prepare 1.0 ml of a mixed solution, and 0.1 ml of the obtained mixed solution was dissolved in 0.5 ml of deuterated chloroform. ¹ H-NMR measurement was performed, and a peak (chemical shift value: 6.08 to 6.10) derived from a proton directly connected to a carbon-carbon double bond of (meth) acrylic acid ester used as a monomer and a solvent It calculated from the change of the ratio of the integral value of the peak (chemical shift value 7.00-7.38 ppm) derived from the proton directly connected to the aromatic ring of toluene used.
¹ H-NMR measurement condition apparatus: JEOL Ltd. nuclear magnetic resonance apparatus “JNM-ECX400”
Solvent: Deuterated chloroform Temperature: 25 ° C

[Mn, molecular weight distribution (Mw / Mn)]
The obtained polymer was subjected to GPC (gel permeation chromatography) measurement, and the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) in terms of standard polystyrene were determined. .
Equipment: GPC equipment "HLC-8220GPC" manufactured by Tosoh Corporation
Separation column: “TSKgel SuperMultipore HZ-M (column diameter = 4.6 mm, column length = 15 cm)” manufactured by Tosoh Corporation
Eluent: Tetrahydrofuran eluent Flow rate: 0.35 ml / min Column temperature: 40 ° C
Detection method: differential refractive index (RI)

[Initiation efficiency of polymerization]
When Mn of the polymer obtained in the following step (1) is Mn (R1) and the polymerization initiation efficiency is 100%, the Mn (calculated value) of the polymer obtained in step (1) is Mn (I1). Then, the polymerization initiation efficiency (F1) in the step (1) is calculated from the following equation.
F1 (%) = 100 × Mn (I1) / Mn (R1)

[Block efficiency from step (1) to step (2)]
The block copolymer obtained in step (2) when Mn of the diblock copolymer obtained in the following step (2) is Mn (R2) and the block efficiency from step 1 to step 2 is 100%. Assuming that Mn (calculated value) is Mn (I2), the block efficiency (F2) from step (1) to step (2) is calculated from the following equation.
F2 (%) = 10000 · {Mn (I2) −Mn (I1)} / [F1 · {Mn (R2) −Mn (R1)}]

[Reference Example 1]
(Step 1: Formation of (meth) acrylic polymer block (a))
After adding 150 ml of toluene to a 300 ml flask whose interior was dried and purged with nitrogen, 1,1,4,7,10,10-hexamethyltriethylenetetramine was added as a Lewis base while stirring the solution in the flask. .74 ml (2.73 mmol), 6.36 ml (2.86 mmol) of a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as the tertiary organoaluminum compound Were sequentially added and then cooled to -20 ° C. To this was added 2.00 ml (2.6 mmol) of a 1.30 mol / L cyclohexane solution of sec-butyllithium as an organic lithium compound, and 1.87 ml of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer. 3.57 ml of a mixture of (7.80 mmol) and 1.66 ml (15.6 mmol) of methyl methacrylate was added all at once to initiate anionic polymerization. After 80 minutes from the end of the monomer addition, the polymerization reaction solution changed from the original yellow color to colorless. Furthermore, the reaction liquid obtained after stirring for 20 minutes was sampled.

  The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in Step 1 was 100%. Moreover, Mn (Mn (R1)) of the obtained polymer was 1,340, and Mw / Mn was 1.16. Furthermore, the polymerization initiation efficiency (F1) in Step 1 was 99%.

(Process 2: (Meth) acrylic polymer block (b) formation)
Subsequently, while stirring the reaction solution at −20 ° C., a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as a tertiary organoaluminum compound was added. 18 ml (1.43 mmol) was added, and 1 minute later, 50.4 ml (350 mmol) of n-butyl acrylate was added as a monomer at a rate of 1 ml / min. The reaction solution was sampled immediately after completion of the monomer addition.

  The consumption rate of n-butyl acrylate in Step 2 was 100%. Moreover, Mn (Mn (R2)) of the obtained diblock copolymer was 21,300, and Mw / Mn was 1.18. Further, the block efficiency (F2) from Step 1 to Step 2 was 88%.

(Step 3: (Meth) acrylic polymer block (a) formation)
Subsequently, while stirring the reaction solution at −20 ° C., 1.63 ml (6.78 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate and 1.44 ml (13.6 mmol) of methyl methacrylate as monomers. ) Was added all at once, and the temperature was raised to 20 ° C. at a rate of 2 ° C./min. After completion of the monomer addition, the reaction solution obtained 60 minutes later was sampled.
The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in Step 3 was 100%.

(Step 4: Termination of anionic polymerization and isolation of (meth) acrylic block copolymer)
Subsequently, 10.0 ml of methanol was added while stirring the reaction solution at 20 ° C. to stop anionic polymerization. The obtained solution was poured into 1 liter of methanol, and the produced polymer was precipitated, recovered by filtration, dried at 100 ° C. and 30 Pa, and 45.2 g of (meth) acrylic block copolymer (A). (Hereinafter referred to as “(meth) acrylic copolymer (A-1)”). Mn of the obtained (meth) acrylic copolymer (A-1) was 22,600, and Mw / Mn was 1.19, and the (meth) acrylic copolymer (A-) determined from GPC and NMR. 1) The number of curable functional groups per molecule was 6.2.

[Production Example 2]
(Step 1: Formation of (meth) acrylic polymer block (a))
After adding 150 ml of toluene to a 300 ml flask whose interior was dried and purged with nitrogen, 1,1,4,7,10,10-hexamethyltriethylenetetramine was added as a Lewis base while stirring the solution in the flask. .74 ml (2.73 mmol), 6.36 ml (2.86 mmol) of a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as the tertiary organoaluminum compound Were sequentially added and then cooled to -20 ° C. To this was added 2.00 ml (2.6 mmol) of a 1.30 mol / L cyclohexane solution of sec-butyllithium as an organolithium compound, and 3.74 ml of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer. 4.57 ml of a mixture of (15.60 mmol) and methyl methacrylate 0.83 ml (7.80 mmol) was added all at once to initiate anionic polymerization. 160 minutes after completion of the monomer addition, the polymerization reaction solution changed from the original yellow color to colorless. Furthermore, the reaction liquid obtained after stirring for 20 minutes was sampled.

  The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in Step 1 was 100%. Further, Mn (Mn (R1)) of the polymer obtained in Step 1 was 1,780, and Mw / Mn was 1.15. Furthermore, the polymerization initiation efficiency (F1) in Step 1 was 98%.

(Process 2: (Meth) acrylic polymer block (b) formation)
Subsequently, while stirring the reaction solution at −20 ° C., a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as a tertiary organoaluminum compound was added. 18 ml (1.43 mmol) was added, and 49.8 ml (346 mmol) of n-butyl acrylate was added as a monomer at a rate of 1 ml / min. The reaction solution was sampled immediately after completion of the addition of n-butyl acrylate.

  The consumption rate of n-butyl acrylate in Step 2 was 100%. Moreover, Mn (Mn (R2)) of the obtained diblock copolymer was 22,800, and Mw / Mn was 1.17. Furthermore, the block efficiency (F2) from Step 1 to Step 2 was 83%.

(Step 3: (Meth) acrylic polymer block (a) formation)
Subsequently, while stirring the reaction solution, a mixture 3 of 3.22-ml (13.4 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer and 0.71 ml (6.71 mmol) of methyl methacrylate was used. .93 ml was added all at once, and then the temperature was raised to 10 ° C. at a rate of 2 ° C./min. The reaction solution was sampled 240 minutes after the addition of the monomer.
The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in Step 3 was 100%.

(Step 4: Termination of anionic polymerization and isolation of (meth) acrylic block copolymer)
Subsequently, 10.0 ml of methanol was added while stirring the reaction solution at −20 ° C. to stop anionic polymerization. The resulting solution was poured into 1 liter of methanol to precipitate the produced (meth) acrylic block copolymer, recovered by filtration, dried at 100 ° C. and 30 Pa, and 46.1 g of (meth) acrylic. A block copolymer (A) (hereinafter referred to as “(meth) acrylic copolymer (A-2)”) was obtained. Mn of the obtained (meth) acrylic copolymer (A-2) was 22,400, and Mw / Mn was 1.21, and the (meth) acrylic copolymer (A-) determined by GPC and NMR was used. 2) The number of curable functional groups per molecule was 12.3.

[Production Example 3]
(Step 1: Formation of (meth) acrylic polymer block (a) precursor)
After adding 150 ml of toluene to a 300 ml flask whose interior was dried and purged with nitrogen, 1,1,4,7,10,10-hexamethyltriethylenetetramine was added as a Lewis base while stirring the solution in the flask. .74 ml (2.73 mmol), 6.36 ml (2.86 mmol) of a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as the tertiary organoaluminum compound Were sequentially added and then cooled to -20 ° C. To this was added 2.00 ml (2.6 mmol) of a 1.30 mol / L cyclohexane solution of sec-butyllithium as an organolithium compound, and 1.70 ml (7.80 mmol) of 4- (trimethylsilyloxy) butyl methacrylate as a monomer. And 3.36 ml of a mixture of 1.66 ml (15.6 mmol) of methyl methacrylate were added all at once to initiate anionic polymerization. After 80 minutes from the end of the monomer addition, the polymerization reaction solution changed from the original yellow color to colorless. After stirring for another 20 minutes, the resulting reaction solution was sampled.

  The consumption rate of 4- (trimethylsilyloxy) butyl methacrylate and methyl methacrylate in Step 1 was 100%. Moreover, Mn (Mn (R1)) of the obtained polymer was 1,300, and Mw / Mn was 1.15. Furthermore, the polymerization initiation efficiency (F1) in Step 1 was 98%.

(Process 2: (Meth) acrylic polymer block (b) formation)
Subsequently, while stirring the reaction solution at −20 ° C., a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as a tertiary organoaluminum compound was added. 18 ml (1.43 mmol) was added, and 1 minute later, 50.4 ml (350 mmol) of n-butyl acrylate was added as a monomer at a rate of 1 ml / min. The reaction solution was sampled immediately after completion of the addition of n-butyl acrylate.

  The consumption rate of n-butyl acrylate in Step 2 was 100%. Moreover, Mn of the obtained diblock copolymer was 21,300 and Mw / Mn was 1.18. Furthermore, the block efficiency (F2) from Step 1 to Step 2 was 100%.

(Process 3: (Meth) acrylic polymer block (a) formation of precursor)
Subsequently, while stirring the reaction solution at −20 ° C., a mixture of 1.48 ml (6.78 mmol) of 4- (trimethylsilyloxy) butyl methacrylate and 1.44 ml (13.6 mmol) of methyl methacrylate as monomers. After 92 ml was added all at once, the temperature was raised to 20 ° C. at a rate of 2 ° C./min. The reaction solution obtained 60 minutes after the addition of the monomer was sampled.

  The consumption rate of 4- (trimethylsilyloxy) butyl methacrylate and methyl methacrylate in Step 3 was 100%. Moreover, Mn of the obtained triblock copolymer was 22,800 and Mw / Mn was 1.17.

(Step 4: Stopping anionic polymerization)
Subsequently, 10.0 ml of methanol was added while stirring the reaction solution at 20 ° C. to stop anionic polymerization.

(Step 5: Introduction of curable functional group (1))
Subsequently, 2.2 ml (26.7 mmol) of dichloroacetic acid was added while stirring the reaction solution at 20 ° C., and the mixture was stirred for 30 minutes. The reaction solution was then poured into 1 liter of methanol to precipitate the polymer, recovered by filtration, and dried at 100 ° C. and 30 Pa to obtain 46.7 g of polymer.

Furthermore, the obtained polymer and 150 ml of toluene were added to a 300 ml flask and dissolved, 9.7 ml (69.6 mmol) of triethylamine was added, and the mixture was cooled in an ice bath. To this was dropped 6.7 ml (69.2 mmol) of methacryloyl chloride, and the mixture was stirred for 2 hours, and then the reaction solution was sampled. ^{When 1} H-NMR measurement was performed, the reaction rate in Step 5 was 95%. Thereafter, 5 ml of methanol was added to stop the reaction. In order to remove the amine salt precipitated from the reaction solution, suction filtration was performed, and then toluene was distilled off from the filtrate. After adding 150 ml of chloroform, washing was performed with an aqueous sodium hydrogen carbonate solution, and the chloroform layer was suction filtered. Next, the chloroform layer was washed 3 times with a saturated saline solution, and magnesium sulfate was added to the chloroform layer to remove water. At 70 ° C., chloroform, triethylamine and methacrylic acid were distilled off to obtain 41.5 g of (meth) acrylic type. A block copolymer (A) (hereinafter referred to as “(meth) acrylic copolymer (A-3)”) was obtained.

  Mn of the obtained (meth) acrylic copolymer (A-3) was 23,100, and Mw / Mn was 1.19, and the (meth) acrylic copolymer (A-) determined from GPC and NMR. 3) The number of curable functional groups per molecule was 5.5.

[Production Example 4]
(Process 1)
After adding 150 ml of toluene to a 300 ml flask whose interior was dried and purged with nitrogen, 1,1,4,7,10,10-hexamethyltriethylenetetramine was added as a Lewis base while stirring the solution in the flask. .74 ml (2.73 mmol), 6.36 ml (2.86 mmol) of a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as the tertiary organoaluminum compound Were sequentially added and then cooled to -20 ° C. To this was added 2.00 ml (2.6 mmol) of a 1.30 mol / L cyclohexane solution of sec-butyllithium as an organolithium compound, and 1.68 ml (7.80 mmol) of 2- (trimethylsilyloxy) ethyl methacrylate as a monomer. And 3.34 ml of a mixture of 1.66 ml (15.6 mmol) of methyl methacrylate were added all at once to initiate anionic polymerization. After 80 minutes from the end of the monomer addition, the polymerization reaction solution changed from the original yellow color to colorless. After stirring for another 20 minutes, the reaction solution was sampled.

  The consumption rate of 2- (trimethylsilyloxy) ethyl methacrylate and methyl methacrylate in Step 1 was 100%. Moreover, Mn (Mn (R1)) of the obtained polymer was 1,300, and Mw / Mn was 1.15. Furthermore, the polymerization initiation efficiency (F1) was 98%.

(Process 2)
Subsequently, while stirring the reaction solution at −20 ° C., a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as a tertiary organoaluminum compound was added. 18 ml (1.43 mmol) was added, and 1 minute later, 50.4 ml (350 mmol) of n-butyl acrylate was added as a monomer at a rate of 1 ml / min. The reaction solution was sampled immediately after completion of the addition of n-butyl acrylate.

  The consumption rate of n-butyl acrylate in Step 2 was 100%. Moreover, Mn (Mn (R2)) of the obtained diblock copolymer was 21,300, and Mw / Mn was 1.18. Furthermore, the block efficiency (F2) from Step 1 to Step 2 was 100%.

(Process 3)
Subsequently, while stirring the reaction solution at −20 ° C., a mixture of 1.46 ml (6.78 mmol) of 2- (trimethylsilyloxy) ethyl methacrylate and 1.44 ml (13.6 mmol) of methyl methacrylate as monomers. After 90 ml was added all at once, the temperature was raised to 20 ° C. at a rate of 2 ° C./min. The reaction solution obtained 60 minutes after the addition of the monomer was sampled.

  The consumption rate of 2- (trimethylsilyloxy) ethyl methacrylate and methyl methacrylate in Step 3 was 100%. Moreover, Mn of the obtained triblock copolymer was 22,800 and Mw / Mn was 1.17.

(Process 4)
Subsequently, while stirring the obtained reaction solution, 10.0 ml of methanol was added at 20 ° C. to stop anionic polymerization.

(Process 5)
Subsequently, 2.2 ml (26.7 mmol) of dichloroacetic acid was added while stirring the reaction solution at 20 ° C., and the mixture was stirred for 30 minutes. The reaction solution was then poured into 1 liter of methanol to precipitate the polymer, recovered by filtration, and dried at 100 ° C. and 30 Pa to obtain 46.0 g of polymer.

Furthermore, the obtained polymer and 150 ml of toluene were added to a 300 ml flask and dissolved, 9.7 ml (69.6 mmol) of triethylamine was added, and the mixture was cooled in an ice bath. To this was dropped 6.7 ml (69.2 mmol) of methacryloyl chloride, and the mixture was stirred for 2 hours, and then the reaction solution was sampled. ^{When 1} H-NMR measurement was performed, the reaction rate in Step 5 was 95%. Thereafter, 5 ml of methanol was added to stop the reaction.

  In order to remove the amine salt precipitated from the reaction solution, suction filtration was performed, and then toluene was distilled off from the filtrate. After adding 150 ml of chloroform, washing was performed with an aqueous sodium hydrogen carbonate solution, and the chloroform layer was suction filtered. Next, the chloroform layer was washed 3 times with a saturated saline solution, and magnesium sulfate was added to the chloroform layer to remove moisture. At 70 ° C., chloroform, triethylamine and methacrylic acid were distilled off to obtain 40.2 g of (meth) acrylic type. A block copolymer (hereinafter referred to as “(meth) acrylic copolymer (A′-1)”) was obtained.

  Mn of the obtained (meth) acrylic copolymer (A′-1) was 23,100, and Mw / Mn was 1.19, and the (meth) acrylic copolymer (A '-1) The number of curable functional groups per molecule was 5.3.

[Production Example 5]
(Process 1)
After adding 150 ml of toluene to a 300 ml flask whose interior was dried and purged with nitrogen, 1,1,4,7,10,10-hexamethyltriethylenetetramine was added as a Lewis base while stirring the solution in the flask. .74 ml (2.73 mmol), 6.36 ml (2.86 mmol) of a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as the tertiary organoaluminum compound Were sequentially added and then cooled to -20 ° C. To this was added 2.00 ml (2.6 mmol) of a 1.30 mol / L cyclohexane solution of sec-butyllithium as an organic lithium compound, and 3.36 ml (15.6 mmol) of 2- (trimethylsilyloxy) ethyl methacrylate as a monomer. And 3.36 ml of a mixture of 0.83 ml (7.80 mmol) of methyl methacrylate was added all at once to initiate anionic polymerization. After 80 minutes from the end of the monomer addition, the polymerization reaction solution changed from the original yellow color to colorless. After stirring for another 20 minutes, the reaction solution was sampled.

  The consumption rate of 2- (trimethylsilyloxy) ethyl methacrylate and methyl methacrylate in Step 1 was 100%. Moreover, Mn (Mn (R1)) of the obtained polymer was 1,700, and Mw / Mn was 1.15. Furthermore, the polymerization initiation efficiency (F1) was 98%.

(Process 2)
Subsequently, while stirring the reaction solution at −20 ° C., a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as a tertiary organoaluminum compound was added. 18 ml (1.43 mmol) was added, and 1 minute later, 49.8 ml (346 mmol) of n-butyl acrylate was added at a rate of 1 ml / min. The reaction solution was sampled immediately after completion of the addition of n-butyl acrylate.

  The consumption rate of n-butyl acrylate in Step 2 was 100%. Moreover, Mn (Mn (R2)) of the obtained diblock copolymer was 22,800, and Mw / Mn was 1.16. Furthermore, the block efficiency (F2) from Step 1 to Step 2 was 100%.

(Process 3)
Subsequently, while stirring the above reaction liquid at −20 ° C., a mixture of 2.96 ml (13.4 mmol) of 2- (trimethylsilyloxy) ethyl methacrylate and 0.72 ml (6.7 mmol) of methyl methacrylate as monomers. After 68 ml was added all at once, the temperature was raised to 20 ° C. at a rate of 2 ° C./min. Sampling was performed 60 minutes after the monomer addition.

  The consumption rate of 2- (trimethylsilyloxy) ethyl methacrylate and methyl methacrylate in Step 3 was 100%. Moreover, Mn of the obtained triblock copolymer was 23,800 and Mw / Mn was 1.17.

(Process 4)
Subsequently, 10.0 ml of methanol was added at 20 ° C. while stirring the reaction solution to stop anionic polymerization.

(Process 5)
Subsequently, 4.4 ml (53.4 mmol) of dichloroacetic acid was added while stirring the reaction solution at 20 ° C., and the mixture was stirred for 30 minutes. The reaction solution was then poured into 1 liter of methanol to precipitate and collect the polymer.

Further, the obtained polymer and 150 ml of toluene were added and dissolved in a 300 ml flask, and 19.4 ml (139.2 mmol) of triethylamine was added and cooled in an ice bath. 13.4 ml (138.4 mmol) of methacryloyl chloride was added dropwise thereto and stirred for 2 hours, and then the reaction solution was sampled. ^{When 1} H-NMR measurement was performed, the reaction rate in Step 5 was 95%. Thereafter, 10 ml of methanol was added to stop the reaction.

  In order to remove the amine salt precipitated from the reaction solution, suction filtration was performed, and then toluene was distilled off from the filtrate. After adding 150 ml of chloroform, washing was performed with an aqueous sodium hydrogen carbonate solution, and the chloroform layer was suction filtered. Next, the chloroform layer was washed three times with a saturated saline solution, and magnesium sulfate was added to the chloroform layer to remove moisture. At 70 ° C., chloroform, triethylamine and methacrylic acid were distilled off to obtain 45.0 g of (meth) acrylic type. A block copolymer (hereinafter referred to as “(meth) acrylic copolymer (A′-2)”) was obtained.

  Mn of the obtained (meth) acrylic copolymer (A′-2) was 23,500 and Mw / Mn was 1.19, and the (meth) acrylic copolymer (A '-2) The number of curable functional groups per molecule was 10.6.

[Production Example 6]
(Step 1: Formation of (meth) acrylic random copolymer)
After adding 150 ml of toluene to a 300 ml flask whose interior was dried and purged with nitrogen, 1,1,4,7,10,10-hexamethyltriethylenetetramine was added as a Lewis base while stirring the solution in the flask. .74 ml (2.73 mmol), 9.54 ml (4.29 mmol) of a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as the tertiary organoaluminum compound Were sequentially added and then cooled to -20 ° C. To this was added 2.00 ml (2.6 mmol) of a 1.30 mol / L cyclohexane solution of sec-butyllithium as an organolithium compound, and 3.50 ml of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer. 57.0 ml of a mixture of (14.58 mmol) and 3.10 ml (29.2 mmol) of methyl methacrylate and 50.4 ml (350 mmol) of n-butyl acrylate were added at a rate of 0.5 ml / min. The reaction solution was sampled immediately after completion of the monomer addition.

The monomer consumption rate was 100%.
(Step 2: Termination of anionic polymerization and isolation of (meth) acrylic random copolymer)
Subsequently, 10.0 ml of methanol was added while stirring the reaction solution at 20 ° C. to stop anionic polymerization. The obtained solution was poured into 1 liter of methanol, the produced polymer was precipitated, recovered by filtration, dried at 100 ° C. and 30 Pa, and 43.5 g of a (meth) acrylic random copolymer (hereinafter, (Meth) acrylic copolymer (A ″ -1)) was obtained. Mn of the obtained (meth) acrylic copolymer (A ″ -1) was 23,100, and Mw / Mn was 1.16, and the (meth) acrylic copolymer obtained from GPC and NMR ( A ″ -1) The number of curable functional groups per molecule was 5.4.

Example 1
[Preparation of curable sealing agent (photo-curable)]
To 100 g of the (meth) acrylic block copolymer (A-1) obtained in Production Example 1, 85 g of methyl acrylate (reactive diluent (1)) and 15 g of acrylic acid (reactive diluent (2)) 4 g of 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator) was added and mixed to prepare a curable sealing agent. The curing rate of the obtained curable sealing agent, the flexibility of the cured product, and the adhesive strength were evaluated as follows. The results are shown in Table 1.

[Curing speed]
The curing rate by UV was evaluated using MARS III manufactured by HAAKE. A high-speed OSC time-dependent measurement mode is used as a measurement mode, a curable sealing agent is applied on a φ20 mm parallel plate, a UV lamp (with a measurement temperature of 25 ° C., a measurement gap of 0.15 mm, and a measurement frequency of 5 Hz). Lumin Dynamics, Omni Cure series 2000, irradiation intensity 150 mW / cm ² ) is measured to measure viscoelasticity, and storage shear modulus (G ′) and loss shear modulus (G ″) are measured for crossover time. did.

[Flexibility of cured product]
The flexibility of the cured product is that a 1 mm thick spacer is placed on the four sides of a release PET film (Toyobo, K1504), a curable sealing agent is poured onto the release PET film, and a PET film is placed thereon. After placing it so as not to contain air bubbles, a UV-irradiating device (HI-TECH, HTE-3000B INTEGRATOR814M) is used to irradiate the release PET film with ultraviolet rays at 5000 mJ / cm ² to provide a curable sealing agent. Using a film prepared by curing, a dynamic viscoelasticity measuring apparatus (Rheogel E-4000, manufactured by UBM Co., Ltd.) was used, and the temperature rising rate was 3 in a temperature-dependent (tensile) mode (frequency: 11 Hz). The storage elastic modulus was measured by raising the temperature from -100 ° C. to 180 ° C., and the storage elastic modulus E ′ ( It was flexibility of the index a).

[Adhesive strength]
A curable sealing agent was applied to an area of 25 × 25 mm ² from a position 5 mm from the end of a glass substrate (width 25 mm × length 100 mm × thickness 2 mm) so that the thickness was 100 μm. Next, another glass substrate of the same size and material was bonded together to produce a shear strength measurement sample coated with a curable sealing agent. This was cured by irradiating with ultraviolet rays at 5000 mJ / cm ² using an ultraviolet irradiation device (manufactured by HI-TECH, HTE-3000B INTEGRATOR 814M) to prepare a sample for measuring shear strength. Using this sample for shear strength measurement, the shear strength was measured by an autograph (manufactured by Shimadzu Corporation, AG-2000B) at 23 ° C. × 55% RH and a shear rate of 50 mm / min.

(Examples 2 and 3 and Comparative Examples 1 to 3)
A curable sealing agent was prepared in the same manner as in Example 1 except that the (meth) acrylic copolymer (A-1) was replaced with the (meth) acrylic copolymer described in Table 1. Then, the curing speed, the flexibility of the cured product, and the adhesive strength were evaluated. The results are shown in Table 1.

Example 4
[Preparation of curable sealing agent (thermosetting type)]
To 100 g of the (meth) acrylic copolymer (A-1) obtained in Production Example 1, 85 g of methyl acrylate (reactive diluent (1)), 15 g of acrylic acid (reactive diluent (2)), IGNOX 1010 (pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals) 1 g, cumene hydroperoxide (thermal polymerization initiator) 0.2 g was added. And mixed to prepare a curable sealing agent. The curing rate of the obtained curable sealing agent, the flexibility of the cured product, and the adhesive strength were evaluated as follows. The results are shown in Table 2.

[Curing speed]
The curing rate by heat was evaluated by the gel fraction after heating at 150 ° C. for 5 minutes. The gel fraction was calculated | required by mass ratio of the hardened | cured material before extraction after uncured partial extraction of hardened | cured material. The uncured part was extracted by immersing the cured product in toluene at room temperature for 24 hours, separating the gel by filtration, and drying at 100 ° C. and 30 Pa.

[Flexibility of cured product]
The flexibility of the cured product is that a 1 mm thick spacer is placed on the four sides of a release PET film (Toyobo, K1504), a curable sealing agent is poured onto the release PET film, and a PET film is placed thereon. After placing so that air bubbles do not enter, using a dynamic viscoelasticity measuring device (Rheogel E-4000, manufactured by UBM Co., Ltd.) using a film prepared by heat treatment at 150 ° C. for 15 minutes and curing. In the temperature-dependent (tensile) mode (frequency: 11 Hz), the temperature rise rate was 3 ° C./min, the temperature was raised from −100 ° C. to 180 ° C., the storage elastic modulus was measured, and the storage elastic modulus E ′ at 25 ° C. (Pa) was used as an index of flexibility.

[Adhesive strength]
The curable sealing agent was applied to an area of 25 × 25 mm ² from a position 5 mm from the end of an aluminum base (width 25 mm × length 100 mm × thickness 2 mm) so that the thickness was 100 μm. Also, dimethylaniline is applied to another aluminum substrate of the same size and material at the same position as above, so that the surface on which two curable sealants are applied and the surface on which dimethylaniline is applied face each other. A sample for measuring shear strength, to which a curable sealing agent was applied, was prepared by bonding. This was heat-treated at 150 ° C. for 15 minutes to be cured, and the shear strength was measured. Thus, in this example, the reducing agent equivalent (dimethylaniline) of the polymerization initiator is applied to the base material as a primer, and a curable sealing agent containing other than the components is applied to the other base material. By bonding these together, a sample for measuring shear strength coated with a curable sealing agent was obtained. Using this sample for shear strength measurement, the shear strength was measured by an autograph (manufactured by Shimadzu Corporation, AG-2000B) at 23 ° C. × 55% RH and a shear rate of 50 mm / min.

(Examples 5 and 6 and Comparative Examples 4 to 6)
A curable sealing agent was prepared in the same manner as in Example 4 except that the (meth) acrylic copolymer (A-1) was replaced with the (meth) acrylic copolymer described in Table 2. Then, the curing speed, the flexibility of the cured product, and the adhesive strength were evaluated. The results are shown in Table 2.

表１および表２から、実施例で得られた硬化型シーリング剤は、接着性が良好であることからシール性に優れ、また、硬化速度および硬化後の柔軟性にも優れることがわかる。

From Table 1 and Table 2, it can be seen that the curable sealing agents obtained in the examples are excellent in sealing properties because of their good adhesiveness, and are excellent in curing speed and flexibility after curing.

Claims (3)

It consists of a (meth) acrylic polymer block (a) having a curable functional group represented by the following general formula (1) and a (meth) acrylic polymer block (b) having no curable functional group. A curable sealing agent comprising a (meth) acrylic block copolymer (A) and a polymerization initiator.

(In the formula, 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 represents O , S, or N (R ⁶ ) (R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), and n represents an integer of 2 to 20)   The curable sealing agent according to claim 1, wherein the polymerization initiator is selected from the group consisting of azo compounds, peroxides and persulfates.   The curable sealing agent according to claim 1 or 2, wherein the (meth) acrylic block copolymer (A) has three or more curable functional groups represented by the general formula (1).