JP2009167346A - Storage stabilization method for active energy ray crosslinking type adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a storage stabilization method for a novel adhesive with a high adhesion strength being excellent in compatibility of respective components constituting the adhesive and outstandingly improving storage stability of the adhesive. <P>SOLUTION: The active energy ray crosslinking type adhesive contains (A) a conjugated diene based oligomer having at least one functional group having a (meth)acryloyl group on a terminal end and having a weight average molecular weight of 500-100,000, and (B) a (meth)acrylic monomer, i.e., a polymerizable compound having a structure represented by general formula (I) at a ratio of 5-500 pts.mass based on 100 pts.mass of it, and contains an active energy ray polymerizable compound containing (C) a specific alkanediol di(meth)acrylate at a ratio of 50-1,000 pts.mass. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an adhesive, and more particularly to a storage stabilization method for an active energy ray-crosslinking adhesive.

  As a method of adhering to rubber using an adhesive, a solvent-type adhesive using water or an organic solvent as a solvent has been widely used as an adhesive containing a rubber component. The reason for using this solvent is to apply the adhesive to the adherend without any gaps, such as by applying it in a liquid state. However, it is necessary to agglomerate the adhesive so that the adhesive part is not destroyed by stress such as dynamic strain. In order to increase the breaking resistance, the solvent is often removed by evaporation or the like in the bonding step of solidifying the adhesive layer. In the case of an adhesive that needs to remove the solvent when solidifying the adhesive layer, the solvent cannot be effectively used as a component after bonding, and it may be necessary to treat the solvent for environmental protection. In many cases, a solventless adhesive or an adhesive in which a solvent is taken into an adhesive layer in an adhesion process for solidifying the adhesive is desired.

As such an adhesive, an adhesive containing a monomer that can be polymerized by irradiation with radiation such as ultraviolet rays, visible light, or an electron beam or external energy such as heat is used. Adhesion methods are known in which adhesion failure due to voids is unlikely to occur on the surface, and the adhesive layer can be network-crosslinked by polymerizing monomers during the adhesion treatment (see, for example, Patent Documents 1 to 3).
In order to obtain a high adhesive force by this bonding method, it is necessary to have excellent application workability of the adhesive, and the components constituting the adhesive are excellent in compatibility with each other, such as gelation during application or storage. There is a demand for an adhesive having excellent storage stability and capable of maintaining a liquid state with little increase in viscosity for a long period of time.

JP-A-55-145768 International Publication No. 2002/09496 Pamphlet JP 2006-328116 A

  Under such circumstances, the present invention has high adhesive strength between the adherend and the adhesive composition, and excellent compatibility of each component constituting the adhesive, and greatly improves the storage stability of the adhesive. It is an object of the present invention to provide a storage and stabilization method for a novel adhesive.

（式中、Ｘは含窒素複素環式基、Ａ、Ａ'及びＡ"は単結合あるいは、−Ｏ−、−Ｓ−、−ＮＨ−結合、Ｒ¹は水素又はメチル基、Ｒ²は炭素数１〜１２の二価の炭化水素基、Ｒ³、Ｒ'³及びＲ"³は単結合、あるいはヘテロ原子を介してＸに結合してもよい炭素数１〜１２の炭化水素基を示し、ｎは１〜３の整数、ｋは０〜２の整数、ｌは０〜２整数でありｎ+ｋ+ｌ≦１〜３であることを示す。）で表される構造を有する重合性化合物（メタ）アクリル系モノマーを５〜５００質量部の割合で含み、かつ（Ｃ）一般式（II）

（式中、Ｒ⁴は炭素数４〜１２のアルカンジイル基を示す。）で表されるアルカンジオール（メタ）ジアクリレートを含む活性エネルギー線重合性化合物を５０〜１０００質量部の割合で含むことを特徴とする活性エネルギー線架橋型接着剤の保存安定化方法、
（２） （Ａ）成分の共役ジエン系オリゴマー１００質量部当り、前記アルカンジオール（メタ）ジアクリレート化合物を２０〜５０質量部含む上記（１）に記載の活性エネルギー線架橋型接着剤の保存安定化方法、
（３） （Ｃ）成分が、（メタ）アクリル系モノマー及び／又はオリゴマーである上記（１）又は（２）の活性エネルギー線架橋型接着剤の保存安定化方法、
（４） （Ｃ）成分が、単官能（メタ）アクリル系モノマー、前記２官能（メタ）アクリル系モノマー及び３官能以上の（メタ）アクリレート系のモノマーの中から選ばれた少なくとも一種である上記（３）に記載の活性エネルギー線架橋型接着剤の保存安定化方法、及び
（５） 上記（１）〜（４）いずれかの活性エネルギー線架橋型接着剤の保存安定化方法によって得られた活性エネルギー線架橋型接着剤、
を提供するものである。 As a result of intensive studies to achieve the above object, the present inventors can achieve the object by adding a specific amount of an alkanediol (meth) diacrylate compound having a specific structure to the adhesive. I found out. The present invention has been completed based on such findings.
That is, the present invention
(1) (A) Conjugated diene oligomer having a weight average molecular weight of 500 to 100,000 having at least one functional group having a (meth) acryloyl group at its terminal, and (B) general formula (I )

(Wherein X is a nitrogen-containing heterocyclic group, A, A ′ and A ″ are single bonds or —O—, —S—, —NH— bonds, R ¹ is hydrogen or a methyl group, and R ² is carbon. A divalent hydrocarbon group having 1 to 12 carbon atoms, R ³ , R ′ ³ and R ″ ³ represent a single bond or a hydrocarbon group having 1 to 12 carbon atoms which may be bonded to X via a hetero atom. , N is an integer of 1 to 3, k is an integer of 0 to 2, l is an integer of 0 to 2, and n + k + l ≦ 1 to 3). Compound (meth) acrylic monomer in a proportion of 5 to 500 parts by mass, and (C) general formula (II)

(In the formula, R ⁴ represents an alkanediyl group having 4 to 12 carbon atoms.) An active energy ray polymerizable compound containing an alkanediol (meth) diacrylate represented by 50 to 1000 parts by mass is included. A storage and stabilization method for an active energy ray-crosslinking adhesive characterized by
(2) Storage stability of the active energy ray-crosslinking adhesive according to (1) above, containing 20 to 50 parts by mass of the alkanediol (meth) diacrylate compound per 100 parts by mass of the conjugated diene oligomer of the component (A). Conversion method,
(3) The method for preservation and stabilization of the active energy ray-crosslinking adhesive according to (1) or (2), wherein the component (C) is a (meth) acrylic monomer and / or oligomer,
(4) The component (C) is at least one selected from a monofunctional (meth) acrylic monomer, the bifunctional (meth) acrylic monomer, and a trifunctional or higher (meth) acrylate monomer. (3) obtained by the storage stabilization method of active energy ray cross-linking adhesive according to (3), and (5) the storage stabilization method of active energy ray cross-linking adhesive of any one of (1) to (4) above. Active energy ray cross-linking adhesive,
Is to provide.

  According to the present invention, the adhesive strength between the adherend and the adhesive composition is high, the compatibility of each component constituting the adhesive is excellent, and the storage stability of the adhesive is improved. Can be provided.

<(A) component>
The active energy ray-crosslinking adhesive of the present invention comprises: (A) a conjugated diene oligomer having a weight average molecular weight of 500 to 100,000 having at least one functional group having a (meth) acryloyl group at its terminal, and 100 parts by mass thereof. (B) General formula (I)

(Wherein X is a nitrogen-containing heterocyclic group, A, A ′ and A ″ are single bonds or —O—, —S—, —NH— bonds, R ¹ is hydrogen or a methyl group, and R ² is carbon. A divalent hydrocarbon group having 1 to 12 carbon atoms, R ³ , R ′ ³ and R ″ ³ represent a single bond or a hydrocarbon group having 1 to 12 carbon atoms which may be bonded to X via a hetero atom. , N is an integer of 1 to 3, k is an integer of 0 to 2, l is an integer of 0 to 2, and n + k + l ≦ 1 to 3). Compound (meth) acrylic monomer in a proportion of 5 to 500 parts by mass, and (C) general formula (II)

(In the formula, R ⁴ represents an alkanediyl group having 4 to 12 carbon atoms.) An active energy ray polymerizable compound containing an alkanediol (meth) diacrylate represented by 50 to 1000 parts by mass is included. Is what you need.

The upper limit of the weight average molecular weight (Mw) of the component (A) is not particularly limited as long as the viscosity of the adhesive becomes too high and it becomes difficult to process, but if it exceeds 100,000, it is difficult to apply the adhesive. May be. On the other hand, if Mw is less than 500, the flexibility of the adhesive after crosslinking with active energy rays is impaired. From this point, the preferable range of Mw is 500 to 100,000.

The conjugated diene oligomer as the component (A) includes a conjugated diene homopolymer, a conjugated diene copolymer, and modified polymers thereof. Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 1,3-hexadiene, and among them, 1,3-butadiene is preferable. As the conjugated diene copolymer, a conjugated diene-aromatic vinyl copolymer is preferable. Examples of the aromatic vinyl monomer include styrene and α-methylstyrene, and among them, styrene is preferable.
The main chain of these conjugated diene oligomers preferably contains a carbon-carbon double bond having a hydrogen atom at the allylic position as a unit in the molecular chain, which tends to be a crosslinking site for sulfur and a crosslinking reaction. Examples of the conjugated diene oligomer in the present invention include polyisoprene, polybutadiene, styrene-butadiene copolymer, and isoprene-butadiene copolymer. The conjugated diene-based oligomer is liquid at the temperature at which the adhesive is blended, and particularly preferably at 0 ° C. or less, the workability and the mixing step of the adhesive are easy, and it is also liquid at a temperature of 50 ° C. or higher. It is preferable that the vapor pressure is low. Even if it is not liquid at the temperature at which the adhesive is blended, there is no particular limitation as long as the conjugated diene oligomer becomes liquid in the adhesive.

<(B) component>
The (meth) acrylate monomer which is the polymerizable compound of component (B) has the following general formula (I)

(Wherein X is a nitrogen-containing heterocyclic group, A, A ′ and A ″ are single bonds or —O—, —S—, —NH— bonds, R ¹ is hydrogen or a methyl group, and R ² is carbon. A divalent hydrocarbon group having 1 to 12 carbon atoms, R ³ , R ′ ³ and R ″ ³ are a single bond or a hydrocarbon group having 1 to 12 carbon atoms which may be bonded to X via a hetero atom, n Represents an integer of 1 to 3.).
In general formula (I), the nitrogen-containing heterocyclic group represented by X is a group derived from an electron-donating nitrogen-containing heterocyclic compound described later. As the divalent hydrocarbon group having 1 to 12 carbon atoms represented by R ^2, for example, a linear or branched alkylene group having 1 to 12 carbon atoms, cycloalkylene group having 5 to 12 carbon atoms, Examples thereof include an arylene group having 6 to 12 carbon atoms and an aralkylene group having 7 to 12 carbon atoms.
Here, as an alkylene group, a C2-C5 linear or branched alkylene group, for example, ethylene group, trimethylene group, propylene group, various butylene groups, etc. are mentioned. Examples of the cycloalkylene group having 5 to 12 carbon atoms include a cyclopentylene group and various cyclohexylene groups, and examples of the arylene group having 6 to 12 carbon atoms include various phenylene groups and various tolylene groups. Examples of the 12 aralkylene group include various benzylene groups and various phenethylene groups.
Among these, a linear or branched alkylene group having 2 to 5 carbon atoms is preferable.
Among R ³ , R ′ ³ and R ″ ³ , the divalent hydrocarbon group having 1 to 12 carbon atoms is, for example, a linear or branched alkylene group having 1 to 12 carbon atoms, or a group having 5 to 12 carbon atoms. Examples thereof include a cycloalkylene group, an arylene group having 6 to 12 carbon atoms, and an aralkylene group having 7 to 12 carbon atoms.
Here, examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a propylene group, various butylene groups, various pentylene groups, and various hexylene groups. The arylene group having 6 to 12 carbon atoms and the aralkylene group having 7 to 12 carbon atoms are the same as in the case of R ² .
A, A ′ and A ″ of the polymerizable compound represented by the general formula (I) are preferably —O—, and R ¹ is preferably a hydrogen atom from the viewpoint of showing high photocurability.

Next, the polymerizable compound represented by the general formula (I) is represented by the following general formula (III):

Wherein X is a nitrogen-containing heterocyclic group, R ³ is a single bond or a hydrocarbon group having 1 to 12 carbon atoms which may be bonded to X via a hetero atom, and D, D ′ and D ″ are Hydroxyl group, mercapto group, amino group or carboxyl group, n is an integer of 1 to 3, k is an integer of 0 to 2, l is an integer of 0 to 2, and n + k + 1 ≦ 1 to 3. The heterocyclic compound (a) represented by the following general formula (IV)

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a divalent hydrocarbon group having 1 to 12 carbon atoms.) An isocyanate group-containing acrylic compound (b) represented by Can be obtained by:
The nitrogen-containing heterocyclic compound (a) represented by the general formula (III) is an electron pair donating basic compound, and is not particularly limited as long as it is a compound containing a nitrogen atom having an unpaired electron. Other heteroatoms such as oxygen and sulfur may be included. Further, it may be a monocyclic compound and a bicyclic compound.

  Examples of nitrogen-containing heterocyclic compounds that are monocyclic and contain only nitrogen include azirine, azeto, azetidine, 1H-pyrrole, 2H-pyrrole, pyrrolidine, 2-imidazoline, 3-imidazoline, 1,2,3-triazole, Pyrazole, imidazole, 1-pyrazoline, 3-pyrazoline, piperidine, pyridine, pyrazine, pyrimidine, pyrazine, 1,2,5 triazine, 1,2,4 triazine, 1H-azepine, 2H-azepine, 3H-azepine, 4H- And azepine.

  In addition, nitrogen-containing heterocyclic compounds containing only nitrogen are indole, benzimidazole, purine, carbazole, β-carboline, quinoline, isoquinoline, sinoline, peteridine, acridine, phenatridineline, quinoxaline. , Phthalazine and the like.

  Nitrogen-containing heterocyclic compounds that are monocyclic and contain nitrogen and other heteroatoms include 3-oxazoline, 2-oxazoline, 4-oxazoline, oxazole, isoxazole, 1,3,4 oxadiazole, 1, Examples include 4-oxazine, morpholine, 2-thiazoline, 3-thiazoline, 4-thiazoline, 1,2,3-thiadiosol, thiazole, isothiazole, 1,4-thiazine, 1,4 thiazan and the like.

Nitrogen-containing heterocyclic compounds that are bicyclic and contain nitrogen and other heteroatoms include:
Examples include benzoxazole, 1H-Furo [3,4-c] pyrazole, phenoxazine, and benzothiazole.

In addition, in order to react with the isocyanate group of the isocyanate group-containing acrylic compound (b) represented by the general formula (IV), the nitrogen-containing heterocyclic compound represented by the general formula (III) It is necessary that at least one functional group such as a hydroxyl group, a mercapto group, an amino group, or a carboxyl group is introduced. The above functional group and isocyanate undergo the following reactions, respectively, and have a photopolymerizable (meth) acryloyl group and a nitrogen-containing heterocyclic group that is an electron-donating basic compound in one molecule. The compounds of the invention can be obtained.
Isocyanate usually reacts with functional groups having various active hydrogens easily at room temperature and pressure. Of the functional groups, a hydroxyl group is preferred. In addition, it is usually preferable that the functional group is bonded to the nitrogen-containing heterocyclic ring via R ³ , but the functional group may be directly bonded to the nitrogen-containing heterocyclic ring. Among these, R ³ , R ′ ³ and R ″ ³ are preferably a methylene group or an ethylene group.

  Examples of the nitrogen-containing heterocyclic compound having a hydroxyl group introduced include 2-pyridylmethanol, 3-pyridylmethanol, 4-pyridylmethanol, 2-chloro-5-hydroxymethylpyridine, 2-hydroxypyridinemethanol, 4-methyl. -5- (2-hydroxyethyl) thiazole, 1- (2-hydroxyethyl) imidazole, 2-butyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 4-methyl-5-hydroxy Examples include pyridine, 8-hydroxyquinoline, 4-hydroxypiperidine and the like. Of these, 4-pyridylmethanol is preferred.

Examples of the nitrogen-containing heterocyclic compound having an amino group introduced include 3-aminomethylpyridine, 2-amino-5-aminomethylpyridine, 3-aminomethyl-6-chloropyridine, 2-aminopyridine, 3-aminopyridine, Examples include aminopyridine, 4-aminopyridine, 4-dimethylaminopyridine, 2-amino-4,6-dimethoxypyridine, and 2-aminothiazole.
Furthermore, examples of the nitrogen-containing heterocyclic compound into which a mercapto group is introduced include 2-mercaptobenzimidazole, mercaptobenzthiazole and the like.

Examples of the nitrogen-containing heterocyclic compound having a carboxyl group introduced include 2-pyridinecarboxylic acid, 3-pyridinecarboxylic acid, 4-pyridinecarboxylic acid, 2,3-pyridinedicarboxylic acid, quinolinecarboxylic acid, and imidazole-4. , 5-dicarboxylic acid, 2,4-dialkylimidazole-5-dithiocarboxylic acid and the like.
Nitrogen-containing heterocyclic compounds into which a plurality of functional groups such as a hydroxyl group, an amino group, and a carboxyl group are introduced include 4-hydroxypyridine-2,6-dicarboxylic acid, 6-hydroxynicotinic acid amide, and 6-aminonicotinic acid. Etc.

  Specific examples of the isocyanate group-containing acrylic compound (b) represented by the general formula (IV) include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 3-acryloyloxypropyl isocyanate, and 3-methacryloyl. And oxypropyl isocyanate. The amount of the (meth) acrylic monomer having an isocyanate group is preferably 1 to 3 equivalents, more preferably 1 to 1 equivalents, relative to the nitrogen-containing heterocyclic compound (a) having the functional group. 5 times equivalent.

Furthermore, the reaction time can be shortened by adding 0.001 to 1% by mass of a tin compound represented by (R ⁴ ) ₂ Sn [OC (═O) R ⁵ ] ₂ as a catalyst to the oligomer. preferable. Here, R ⁴ is an alkyl group having 1 to 6 carbon atoms or an optionally substituted phenyl group, and R ⁵ represents an alkyl group having 1 to 23 carbon atoms. A typical example of the catalyst is di-n-butyltin dilaurate.
The solvent used in the reaction is not particularly limited as long as it is inert. Toluene, xylene and the like are preferable for handling.
The reaction temperature is usually room temperature to 100 ° C., and the reaction time is usually about 5 minutes to 10 hours.
Through the above steps, the polymerizable compound is a component (B) having a photopolymerizable (meth) acryloyl group and a nitrogen-containing heterocyclic group which is an electron pair donating basic compound in one molecule ( A (meth) acrylate monomer can be obtained.
The polymerizable compound (B) is preferably contained in an amount of 20 to 400 parts by mass per 100 parts by mass of the conjugated diene polymer (A). If it exists in the range of 20-400 mass parts, the viscosity adjustment effect by (B) component can be show | played.

<(C) component>
The said adhesive agent needs to contain the active energy ray polymeric compound of (C) component in the ratio of 50-1000 mass parts with respect to 100 mass parts of conjugated diene oligomers. By containing the active energy ray-polymerizable compound in the above range, the adhesive is maintained in a liquid state and excellent in applicability to the adherend, and good adhesiveness can be obtained. Among the components (C), the general formula (II)

(In the formula, R ⁴ represents an alkanediyl group having 4 to 12 carbon atoms.) The alkanediol (meth) diacrylate compound represented by the formula (C) must be included, and the content thereof is the total mass of the component (C). On the other hand, it is preferable that it is the range of 50-100 mass%, and it is preferable that 20-50 mass parts of alkanediol (meth) diacrylate compounds are contained with respect to 100 mass parts of conjugated diene oligomers of (A) component. By containing the alkanediol (meth) diacrylate compound in the above range, the compatibility of each component constituting the adhesive is excellent, and it does not cause gelation during coating or storage, and it is a liquid with little increase in viscosity for a long time. An adhesive having excellent storage stability that can maintain the state can be obtained.

In the adhesive of the present invention, the component (C) is preferably a (meth) acrylic monomer and / or oligomer.
Examples of the acrylic oligomer include polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polybutadiene acrylate, and silicone acrylate. Here, examples of the polyester acrylate oligomer include esterification of hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of polyvalent carboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The epoxy acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. A carboxyl-modified epoxy acrylate oligomer obtained by partially modifying this epoxy acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. It can be obtained by esterifying the hydroxyl group of ether polyol with (meth) acrylic acid.

In addition, as acrylate oligomers, polybutadiene oligomers with high hydrophobicity with acrylate groups in the side chain of polybutadiene oligomers, silicone acrylate oligomers with polysiloxane bonds in the main chain, many reactivity in small molecules There are aminoplast resin acrylate oligomers obtained by modifying aminoplast resins having a group.
The weight average molecular weight of the acrylate oligomer is a value in terms of standard polymethyl methacrylate measured by GPC method, preferably 500 to 100,000, more preferably 1,000 to 70,000, still more preferably 3,000 to 40,000. 000 is selected.

Further, the component (C) is at least one selected from a monofunctional (meth) acrylic monomer, a bifunctional (meth) acrylic monomer, and a trifunctional or higher (meth) acrylate monomer. Good.
Examples of monofunctional acrylic monomers include acrylates such as cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate.
Examples of the bifunctional acrylic monomer that is an alkanediol (meth) diacrylate compound represented by the general formula (II) include 1,4-butanediol di (meth) acrylate and 1,5-pentanediol di (meth) acrylate. 1,6-hexanediol di (meth) acrylate, 1,7 heptanediol di (meth) acrylate, 1,8 octanediol di (meth) acrylate, 1,9 nonanediol di (meth) acrylate, 1,10 decane Tricyclodecane dimethanol di (meth), including diol di (meth) acrylate, 1,11 undecanediol di (meth) acrylate, 1,12 dodecanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, cycloalkane Acrylate (made by Shin-Nakamura Chemical Co., Ltd.) A-DCP) and the like.
Such monofunctional and bifunctional acrylic monomers are used as viscosity modifiers.

  Examples of tri- or more functional acrylic monomers include trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide Modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate Etc.

  Examples of the tri- or higher functional acrylic monomer include commercially available pentaerythritol polyethoxy acrylate (trademark “KAYARAD THE-330” manufactured by Nippon Kayaku Co., Ltd.), pentaerythritol polypropoxy acrylate ( Made by the same company, trademark “KAYARAD TPA-320”; produced by the same company, trademark “KAYARAD TPA-330”), dipentaerythritol polyacrylate (trade name “Beamset 700” manufactured by Arakawa Chemical Industries, Ltd.), pentaerythritol polyacrylate (Trademark “Beamset 710” manufactured by the same company).

(C) Component acrylate monomers and oligomers are mainly used as viscosity modifiers and solubility parameter (SP value) modifiers with adherends, and monomers having acrylate functional groups 1 and 2 (C1) The monomer having 3 or more acrylate functional groups is (C2) and the oligomer having an acrylate functional group is (C3), which can be appropriately selected depending on the viscosity of the adhesive of the present invention. Moreover, each can be mixed and used.
Usually, (C1) is mainly used as a viscosity modifier.
The preferable viscosity of the adhesive is 2000 mPa · s or less.

In the active energy ray cross-linking adhesive of the present invention containing the component (A), the component (B) and the component (C), both components have a (meth) acryloyl group or an active energy ray polymerizable compound in the molecule. Therefore, it has the property of being crosslinked and cured by irradiation with active energy rays.
The active energy ray in the present invention refers to an electromagnetic wave or a charged particle beam having energy quanta, and examples thereof include ultraviolet rays and electron beams as typical examples.
Ultraviolet rays are obtained with a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, etc., and the irradiation amount is usually 100 to 3000 mJ / cm ² , while the electron beam is obtained with an electron beam accelerator or the like, and the irradiation amount is usually 2-50 MRad.
In addition, when using an electron beam, a cured resin layer can be obtained, without adding a photoinitiator.
The photopolymerization initiator is used as desired when active light such as ultraviolet rays is used as the active energy ray.
Examples of the photopolymerization initiator include 2,4 diethylthioxanthone, p-dimethylaminobenzoic acid isoamyl ester, benzoin alkyl ethers such as benzoin, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; , 2-dimethoxy-2-phenylacetophenone, benzophenone, benzyl, diacetyl, diphenyl sulfide, eosin, thionine, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone and the like.
The photopolymerization initiator is preferably blended in an amount of 0.1 to 10 parts by mass per 100 parts by mass of the conjugated diene polymer (A).

In the present invention, the material of the adherend bonded to rubber is not particularly limited, but thermoplastics are preferred. Examples of the thermoplastics include polyamides such as polyamide, polyester, polypropylene, and polyethylene; styrene resins such as polycarbonate, polyacrylate, and ABS resin; and vinyl chloride resins. Polyester is particularly preferred because it is high and is relatively difficult to adhere to rubber by conventional methods.
The form of the plastic adherend used in the present invention may be any of a film, a fiber, a nonwoven fabric, a monofilament cord, and a multifilament cord, and may be an extruded product or an injection molded product.

  In the bonding method using the adhesive of the present invention, first, at least a part of the surface of the adherend, for example, one surface of the sheet-like adherend, is immersed, brushed, cast, sprayed, roll coated, knife A coating film of the adhesive is formed by application or the like. Such a surface of the adherend may be pretreated by electron beam, microwave, corona discharge, plasma treatment or the like. The thickness of the adhesive layer is preferably 0.5 to 50 μm, particularly preferably 1 to 10 μm.

  The rubber component used in the present invention is not particularly limited. For example, natural rubber; polyisoprene synthetic rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene rubber (NBR). ), Conjugated diene-based synthetic rubbers such as chloroprene rubber (CR) and butyl rubber (IIR); ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene copolymer rubber (EPDM), polysiloxane rubber, etc. Of these, natural rubber and conjugated diene synthetic rubber are preferred. Moreover, you may use rubber | gum in combination of 2 or more types.

The vulcanization of these rubbers is, for example, sulfur; a tyrlium polysulfide compound such as tetramethyltyrarium disulfide or dipentamethylenetyrarium tetrasulfide; 4,4-dithiomorpholine; p-quinonedioxime; p, p′- Dibenzoquinone dioxime; cyclic sulfur imide; peroxide can be used as a vulcanizing agent, but sulfur is preferred.
In addition to the above ingredients, rubber contains various compounding agents such as carbon black, silica, aluminum hydroxide and other filler vulcanization accelerators, anti-aging agents, and softeners that are commonly used in the rubber industry. can do. Furthermore, it is good also as a composite_body | complex with the particle | grains, fiber, cloth, etc. of various materials.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
<Synthesis Example 1>
Component (B): Synthesis of polymerizable compound (meth) acrylic monomer A 500 ml round bottom flask equipped with a condenser was charged with 250 g of toluene as a solvent, 100 g of 4-hydroxymethylpyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) and di as a catalyst. -0.005 g of n-butyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved. Subsequently, 142.3 g of 2-acryloyloxyethyl isocyanate (trade name Karenz AOI manufactured by Showa Denko KK) was added. Heating and stirring were performed in a water bath with a stirrer (1.5 hr at 65 ° C.). After removing from the water bath and cooling, toluene was removed by vacuum distillation. The obtained product was 239.7 g.

（Ｂ）成分：ピリジンメタアクリレート、合成例１で得られたもの

（Ｃ）成分（２官能）：ポリプロピレングリコール＃４００ジアクリレート（ＰＯ７ｍｏｌ）（新中村化学工業（株）製 商標「ＡＰＧ−４００」）

（Ｃ）成分（２官能）１，６−ヘキサンジオールジ（メタ）アクリレート

（Ｃ）成分（２官能）１，１０デカンジオールジ（メタ）アクリレート

（Ｃ）成分（多官能）ペンタエリスリトールポリエトキシアクリレート（日本化薬（株）製の商標「ＫＡＹＡＲＡＤ ＴＨＥ−３３０」）

1. Compatibility evaluation of each component constituting the adhesive The compatibility was evaluated for each of the following components (A), (B) and (C) which are the components of the adhesive used in the present invention. . The evaluation results are shown in Table 1.
Component (A): Acrylic polybutadiene having an acryloyl group (CH ₂ ═CHCO—) introduced at the end of the butadiene polymer, a trade mark “BAC-45” manufactured by Osaka Organic Chemical Industry Co., Ltd. (Mw = 2800 of polybutadiene moiety, (Viscosity = 3.4 Pa · s, saponification number = about 49)

Component (B): pyridine methacrylate, obtained in Synthesis Example 1

(C) Component (bifunctional): Polypropylene glycol # 400 diacrylate (PO 7 mol) (trade name “APG-400” manufactured by Shin-Nakamura Chemical Co., Ltd.)

(C) Component (bifunctional) 1,6-hexanediol di (meth) acrylate

(C) Component (bifunctional) 1,10 decanediol di (meth) acrylate

(C) component (polyfunctional) pentaerythritol polyethoxy acrylate (trademark “KAYARAD THE-330” manufactured by Nippon Kayaku Co., Ltd.)

As shown in Table 1, (A) component acrylated polybutadiene “BAC-45” and (B
The compatibility of the component pyridine methacrylate, the (C) component (bifunctional) “APG-400” and the (C) component (polyfunctional) “THE-330” was insoluble.
Further, the compatibility of (B) component pyridine methacrylate and (C) component “APG-400” and “THE-330” was separated with the initial compatibility (lightening red) time.
On the other hand, the combination of component (C) used in the adhesive of the present invention with 1,6-hexanediol di (meth) acrylate and 1,10 decanediol di (meth) acrylate was compatible in both cases. It was.

Examples 1 to 3 and Comparative Example 1
Four types of adhesives were prepared based on the formulation described in Table 2, and the storage stability of the adhesives was evaluated. The storage stability was evaluated by the viscosity at 25 ° C. (mPa · s).
The viscosity was measured with a rotational viscometer.
Probe: No.4, rotation speed: 60rpm, measurement time: 60 seconds

［注］
＊１：トリシクロデカンジメタノールジアクリレート
＊２：ポリプロピレングリコール♯４００ジアクリレート
＊３：ペンタエリスリトールポリエトキシアクリレート
＊４：２，４−-ジエチルチオキサントン

[note]
* 1: Tricyclodecane dimethanol diacrylate * 2: Polypropylene glycol # 400 diacrylate * 3: Pentaerythritol polyethoxyacrylate * 4: 2,4-Diethylthioxanthone

第３表から分かるように接着剤に２官能のアルカンジオール（メタ）ジアクリレート化合物を配合した実施例１〜３の接着剤は、２５℃で６０日間保存すると多少の粘度上昇は認められるものの比較例１に比べて非常に優れた保存安定性を示すことが分かる。

As can be seen from Table 3, the adhesives of Examples 1 to 3 in which a bifunctional alkanediol (meth) diacrylate compound was blended with the adhesive were compared with each other although some viscosity increase was observed when stored at 25 ° C. for 60 days. It can be seen that the storage stability is much better than that of Example 1.

  According to the present invention, the adhesive strength between the adherend and the adhesive composition is high, and the compatibility of each component constituting the adhesive is excellent, so that the storage stability of the adhesive is greatly improved. Low viscosity of the adhesive can be achieved. Therefore, the adhesive obtained by the method of the present invention can be effectively applied to the production of rubber reinforcements, rubber articles and tires that require adhesion between rubber and adherend.

Claims (5)

(A) Conjugated diene oligomer having a weight average molecular weight of 500 to 100,000 having at least one functional group having a (meth) acryloyl group at its terminal, and (B) the general formula (I) per 100 parts by mass thereof

(Wherein X is a nitrogen-containing heterocyclic group, A, A ′ and A ″ are single bonds or —O—, —S—, —NH— bonds, R ¹ is hydrogen or a methyl group, and R ² is carbon. A divalent hydrocarbon group having 1 to 12 carbon atoms, R ³ , R ′ ³ and R ″ ³ represent a single bond or a hydrocarbon group having 1 to 12 carbon atoms which may be bonded to X via a hetero atom. , N is an integer of 1 to 3, k is an integer of 0 to 2, l is an integer of 0 to 2, and n + k + l ≦ 1 to 3). Compound (meth) acrylic monomer in a proportion of 5 to 500 parts by mass, and (C) general formula (II)

(In the formula, R ⁴ represents an alkanediyl group having 4 to 12 carbon atoms.) An active energy ray polymerizable compound containing an alkanediol (meth) diacrylate represented by 50 to 1000 parts by mass is included. A storage and stabilization method for an active energy ray-crosslinking adhesive characterized by the following.   The method for stabilizing and stabilizing an active energy ray-crosslinking adhesive according to claim 1, comprising 20 to 50 parts by mass of the alkanediol (meth) diacrylate compound per 100 parts by mass of the conjugated diene oligomer of component (A).   (C) A component is a (meth) acrylic-type monomer and / or oligomer, The storage stabilization method of the active energy ray bridge | crosslinking type adhesive agent of Claim 1 or 2. The component (C) is at least one selected from a monofunctional (meth) acrylic monomer, the bifunctional (meth) acrylic monomer, and a trifunctional or higher (meth) acrylate monomer. A storage stabilization method for the active energy ray-crosslinking adhesive according to claim.   An active energy ray cross-linking adhesive obtained by the storage stabilization method for an active energy ray cross-linking adhesive according to any one of claims 1 to 4.