JP5676256B2 - Adhesive composition for difficult-to-adhere substrate, adhesive using the same, and optical disk device - Google Patents

Description

The present invention relates to an adhesive composition for a difficult-to-adhere substrate, an adhesive using the same, and an optical disk device. More specifically, a reactive oligomer having a (meth) acryloyl group, at least one aliphatic branched structure and an alicyclic aliphatic structure in the molecule, and one (meth) acryloyl group at the molecular end. The present invention relates to an adhesive composition for difficult-to-adhere base materials containing the above-described compounds as essential components.

With the development of electronics technology and optical technology, various optoelectronic technologies and products are flourishing. In particular, in recent years, optical disk devices for recording / reproducing next-generation optical discs such as Blu-ray discs (BD) having a recording density higher than that of compact discs (CDs) and digital versatile discs (DVDs) are rapidly spreading. doing.

In general, an optical disk device is provided with an optical pickup device that reads information (optical signal) recorded on a recording medium. In the case of a CD or DVD, the optical pickup device is assembled and fixed from the viewpoint of processability by UV. An adhesive that is cured using an active energy ray such as is used (Patent Document 1).

The same process should be applied to BD, but in the case of BD, the transmitted optical signal is much finer than that of CD or DVD, so that a very high design accuracy is required for assembling the device. Is done. Therefore, in assembling the BD optical pickup device, there is a demand for an adhesive that does not cause misalignment during assembly, that is, has less shrinkage during curing.

The substrate of the optical pickup device is made of cycloolefin polymer (COP) or glass for the lens, and polyphenylene sulfide (PPS), liquid crystal polymer (LCP) or magnesium alloy for the peripheral materials (lens holder, housing, etc.). Often used. These materials, particularly COP, PPS, and LCP, are often difficult to bond due to surface energy problems inherent in the polymer, and the adhesive may be required to have high adhesion to these substrates.

From the above, it can be said that the adhesive necessary for adhesive fixing of the optical pickup device is required to have low curing shrinkage and high adhesion to the target adhesive substrate.

JP 2007-334999 A

The present invention provides an adhesive composition having high adhesion to difficult-to-adhere substrates such as COP, PPS, and LCP, and further an adhesive composition having cure shrinkage suitable for manufacturing an optical disk device. The purpose is to provide.

As a result of intensive studies by the inventors to solve the above problems, the present invention comprises a specific reactive oligomer and a specific compound having at least one aliphatic branched structure and alicyclic aliphatic structure in the molecule. The present inventors have devised an adhesive composition for a difficult-to-adhere substrate and have completed the present invention.

That is, the present invention
(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
And (B) at least one aliphatic branched structure and an alicyclic aliphatic structure in the molecule, and the general formula (2):
—OC (O) C (R ^b ) ═CH ₂ (2)
(Wherein R ^b represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
The present invention relates to an adhesive composition for difficult-to-adhere substrates, comprising as an essential component a compound having at least one group represented by the formula:

The aliphatic branched structure of the component (B) is preferably a t-butyl group.

The reactive oligomer of component (A) is a vinyl polymer having two or more groups represented by the general formula (1) per molecule and having one or more substituents at the molecular ends. preferable.

Furthermore, (C) general formula (3):
—OC (O) C (R ^c ) ═CH ₂ (3)
(Wherein R ^c represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
It is preferable to contain a vinyl polymer having 1 or less at the molecular terminal per molecule on average.

Furthermore, it is preferable to contain (D) a polymerization initiator.

The component (D) is preferably a radical photopolymerization initiator.

The molecular weight distribution of the component (A) and / or the component (C) is preferably less than 1.8.

It is preferable that the component (A) and / or the component (C) is a (meth) acrylic polymer.

Furthermore, it is preferable to contain (E) a filler.

Moreover, this invention relates to the adhesive agent which used the said adhesive composition for difficult-to-adhere base materials as a main component.

The adhesive preferably uses polyphenylene sulfide, polycycloolefin, liquid crystal polymer, or magnesium alloy as an adherend.

The adhesive is preferably used for bonding an optical member.

The adhesive is preferably used for manufacturing an optical disk device.

Furthermore, the present invention relates to an optical disc apparatus manufactured using the adhesive.

In the present invention, since it is an adhesive composition for a difficult-to-adhere substrate comprising a specific reactive oligomer and a specific compound having at least one aliphatic branched structure and alicyclic aliphatic structure in the molecule, High adhesion to materials such as COP, PPS, LCP.

Hereinafter, the adhesive composition for difficult-to-bond substrates of the present invention will be described in detail.

<(A) component>
The component (A) is represented by the general formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
Is a reactive oligomer having more than one group ((meth) acryloyl group) represented by From the viewpoint of curability and processability, it is preferably a photo-radical curable oligomer, and it is preferable to have two or more (meth) acryloyl groups from the viewpoint of crosslinking. Here, the term “two or more” means that all the components (A) do not have to have two or more (meth) acryloyl groups, preferably 1.2 or more on average, more preferably 1.5 or more, More preferably, it may be 1.7 or more. The number of (meth) acryloyl groups is preferably 10 or less, more preferably 6 or less, and even more preferably 5 or less.

At least one of the (meth) acryloyl group is present at the molecular terminal of the vinyl polymer from the viewpoint of obtaining rubber elasticity by making the molecular weight between cross-linking points uniform and large, preferably 500 to 100,000. And preferably present at both ends.

R ^a in the (meth) acryloyl group represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

Examples of the organic group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a nitrile group. You may have the substituent of. 1-18 are preferable and, as for carbon number of an organic group, 1-16 are more preferable.

Examples of the alkyl group having 1 to 20 carbon atoms include aryl groups having 6 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group. Examples of the aralkyl group having 7 to 20 carbon atoms such as phenyl group and naphthyl group include benzyl group and phenylethyl group.

Specific examples of R ^a include, for example, —H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), —C ₆ H ₅ , —CH. ₂ OH, —CN and the like are preferable, and —H and —CH ₃ are more preferable.

(A) There is no limitation in particular in the vinyl-type monomer which comprises the principal chain of a component, Various things can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Acid toluyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic 3-methoxybutyl acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxy) propyltrimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid 2 -Perfluoroethylethyl, 2- (perfluoroethyl) 2- (perfluoroethyl) (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, di (meth) acrylate Perfluoromethyl methyl, 2-meth (meth) acrylic acid Such as fluoromethyl-2-perfluoroethylethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, ) Acrylic monomers; aromatic vinyl monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, vinylidene fluoride; Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid and di Kill esters; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; containing nitrile groups such as acrylonitrile and methacrylonitrile Vinyl monomers; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene And conjugated dienes such as isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or in combination. Of these, aromatic vinyl monomers and (meth) acrylic monomers are preferred from the viewpoint of physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, and more preferred are butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. Furthermore, from the viewpoint of compatibility and adhesiveness of the obtained adhesive, the vinyl monomer constituting the main chain may contain at least two selected from butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. Particularly preferred.

Examples of the reactive oligomer (A) include epoxy acrylate resins such as bisphenol A type epoxy acrylate resins, phenol novolac type epoxy acrylate resins, and cresol novolak type epoxy acrylate resins, and epoxy acrylate types such as COOH group-modified epoxy acrylate resins. Resin, polyol (polytetramethylene glycol, polyester diol of ethylene glycol and adipic acid, ε-caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc. ) And organic isocyanates (tolylene diisocyanate, isophorone diisocyanate, diphe Urethane resins obtained from methane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, etc.) (hydroxy) -containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meda) acrylate, pentaerythritol Urethane acrylate resins obtained by reacting triacrylate, etc., resins in which a (meth) acryloyl group is introduced into the polyol via an ester bond, polyester acrylate resins, polyacryl acrylate resins, and the like. Among these, from the viewpoint of low viscosity, low curing shrinkage, and flexibility, it is preferable to use a polyacrylacrylate resin, and it is more preferable to use a polyacrylacrylate resin.

On the other hand, from the viewpoint of the availability of production raw materials and physical property control, urethane acrylate resins obtained by reacting the above-mentioned modified polyol and urethane resin obtained from organic isocyanate with a hydroxyl group-containing (meth) acrylate are used. It is preferable to use it.

In the present invention, these preferable monomers may be copolymerized with the other monomers, and in this case, it is preferable that these preferable monomers are contained in a weight ratio of 40% or more.

The component (A) is preferably a (meth) acrylic polymer in terms of adhesion to a difficult-to-adhere substrate, heat resistance, and weather resistance.

The molecular weight distribution of component (A) (ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC)) is not particularly limited, but preferably less than 1.8. More preferably, it is 1.7 or less, more preferably 1.6 or less, particularly preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less.

In the GPC measurement in the present invention, a polystyrene gel column is usually used with chloroform or tetrahydrofuran as a mobile phase, and the molecular weight value is obtained in terms of polystyrene.

The lower limit of the number average molecular weight of the component (A) is preferably 500, more preferably 3,000, and the upper limit is preferably 100,000, more preferably 40,000. If the molecular weight is less than 500, the original characteristics of the vinyl polymer tend to be hardly expressed, and if it exceeds 100,000, handling tends to be difficult.

<(C) component>
The component (C) has the general formula (3)
—OC (O) C (R ^c ) ═CH ₂ (3)
(Wherein R ^c represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
Is a vinyl polymer having, on average, one or less groups ((meth) acryloyl group) represented by It is preferable from the viewpoint of rubber elasticity after curing that it has one (meth) acryloyl group and the substituent is present at the molecular end. For R ^c is the same as the above ^{R a} is illustrated.

The (meth) acryloyl group is preferably 0.5 or more, and more preferably 0.7 or more. When the amount is less than these ranges, there are many unreacted portions remaining and it is difficult to obtain a cured product for the purpose.

The vinyl monomer constituting the main chain of the component (C) is not particularly limited, and various types can be used. As a specific example, the same vinyl monomer that constitutes the main chain of the component (A) can be used, and the vinyl monomer that constitutes the main chain of the component (A) can also be used and preferred vinyl monomers and the like. The same. The component (C) is preferably a (meth) acrylic polymer in terms of adhesion to a hardly-adhesive substrate, heat resistance and weather resistance.

The molecular weight distribution of component (C) (ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC)) is not particularly limited, but is preferably less than 1.8. More preferably, it is 1.7 or less, more preferably 1.6 or less, particularly preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less.

The lower limit of the number average molecular weight of the component (C) is preferably 500, more preferably 2,000, and the upper limit is preferably 100,000, more preferably 40,000. If the molecular weight is less than 500, the original characteristics of the vinyl polymer tend to be hardly expressed, and if it exceeds 100,000, handling tends to be difficult.

In addition, since (C) component has the objective to reduce the viscosity of a composition, it is preferable that the viscosity in 23 degreeC is 100 Pa.s or less.

Although there is no limitation in particular in the usage-amount of (C) component, it is preferable that it is 5-200 parts with respect to 100 parts of (A) component (weight part, hereafter the same), and it is further more preferable that it is 10-100 parts. . When the amount is less than 5 parts, the effect of reducing the viscosity of the composition is small, and when it exceeds 200 parts, the curability tends to be low.

<Production method of component (A) and component (C)>
There is no limitation in particular about the manufacturing method of (A) component and (C) component.

The vinyl polymer is generally produced by anionic polymerization or radical polymerization, and radical polymerization is preferred because of the versatility of the monomer or ease of control. Among radical polymerizations, it is preferably produced by living radical polymerization or radical polymerization using a chain transfer agent, and the former is particularly preferable.

The radical polymerization method used for the production of the component (A) and the component (C) uses an azo compound, a peroxide, or the like as a polymerization initiator, and a monomer having a specific functional group and a vinyl monomer are simply co-polymerized. It can be classified into “general radical polymerization method” for polymerization and “controlled radical polymerization method” in which a specific functional group can be introduced at a controlled position such as a terminal.

The “general radical polymerization method” is a simple method. However, in this method, a monomer having a specific functional group is introduced into the polymer only in a probabilistic manner, so an attempt is made to obtain a polymer having a high functionalization rate. In such a case, it is necessary to use this monomer in a considerably large amount, and conversely, in the case of using a small amount, there is a problem that the proportion of the polymer in which this specific functional group is not introduced becomes large. Moreover, since it is free radical polymerization, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

The “controlled radical polymerization method” further includes a “chain transfer agent method” in which a vinyl polymer having a functional group at a terminal is obtained by polymerization using a chain transfer agent having a specific functional group, It can be classified as “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be obtained by growing the terminal without causing a termination reaction or the like.

In the “chain transfer agent method”, a polymer having a high functionalization rate can be obtained, but a chain transfer agent having a considerably large amount of a specific functional group with respect to the initiator is required. There is an economic problem. Further, like the above-mentioned “general radical polymerization method”, there is also a problem that only a polymer having a wide molecular weight distribution and high viscosity can be obtained because of free radical polymerization.

Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization that is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. It is difficult to obtain a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5), and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

Therefore, the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. The production method of the vinyl polymer having the specific functional group is more preferable.

In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. Pseudo-living polymerization in which is grown while in equilibrium. The definition in the present invention is also the latter.

The “living radical polymerization method” has been actively researched by various groups in recent years.

Examples thereof include those using a cobalt porphyrin complex as shown in Journal of the American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943, “Atom transfer radical polymerization” using radical scavengers such as nitroxide compounds as shown in Macromolecules, 1994, 27, 7228, organic halides as initiators and transition metal complexes as catalysts. (Atom Transfer Radical Polymerization: ATRP).

Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above-mentioned “living radical polymerization method”. In addition to the characteristics of ”, it has a halogen, which is relatively advantageous for functional group conversion reaction, at the end, and has a high degree of freedom in designing initiators and catalysts. Therefore, production of vinyl polymers having specific functional groups The method is more preferable.

Examples of the atom transfer radical polymerization method include, for example, Matyjazewski et al., Journal of the American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules. 1995, 28, 7901, Science 1996, 272, 866, WO96 / 30421 pamphlet, WO97 / 18247 pamphlet or Sawamoto et al., Macromolecules 1995, 28, And the method described on page 1721.

In the present invention, there is no particular restriction as to which of these methods is used, but basically, a controlled radical polymerization method is used, and a living radical polymerization method is preferred from the standpoint of ease of control, and particularly an atom. The transfer radical polymerization method is preferred.

First, one of the controlled radical polymerization methods, a polymerization method using a chain transfer agent will be described.

The radical polymerization using a chain transfer agent (telomer) is not particularly limited, but the following two methods are exemplified as a method for obtaining a vinyl polymer having a terminal structure suitable for the present invention.

JP-A-4-132706 discloses a method for obtaining a halogen-terminated polymer by using a halogenated hydrocarbon as a chain transfer agent, JP-A-61-271306, JP-A-2594402, This is a method of obtaining a hydroxyl-terminated polymer by using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent as disclosed in JP-A-54-47782.

Next, the living radical polymerization method will be described. First, a method using a radical scavenger (capping agent) such as a nitroxide compound will be described.

In this polymerization method, a stable nitroxy free radical (= N—O.) Is generally used as a radical capping agent. Such compounds are not particularly limited, but are cyclic such as 2,2,6,6-substituted-1-piperidinyloxy radical and 2,2,5,5-substituted-1-pyrrolidinyloxy radical. Nitroxy free radicals from hydroxyamines are preferred. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable.

Specific examples of the nitroxy free radical compound include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl- 1-piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, Examples thereof include 1,1,3,3-tetramethyl-2-isoindolinyloxy radical and N, N-di-t-butylamineoxy radical.

Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used.

The radical capping agent is used in combination with a radical generator. It is considered that the reaction product of the radical capping agent and the radical generator serves as a polymerization initiator and the polymerization of the addition polymerizable monomer proceeds.

Although there is no limitation in the usage rate of both, 0.1-10 mol of radical initiators are suitable with respect to 1 mol of radical capping agents.

As the radical generator, various compounds can be used, but a peroxide capable of generating a radical under the polymerization temperature condition is preferable.

The peroxide is not particularly limited, but diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diisopropyl peroxydicarbonate, Examples thereof include peroxycarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate, alkyl peresters such as t-butylperoxyoctoate and t-butylperoxybenzoate. Benzoyl peroxide is particularly preferable.

Furthermore, radical generators such as radical-generating azo compounds such as azobisisobutyronitrile may be used instead of peroxide.

As reported in Macromolecules 1995, 28, 2993, instead of using a radical capping agent and a radical generator together, the following alkoxyamine compound may be used as an initiator. I do not care.

When an alkoxyamine compound is used as an initiator, a polymer having a functional group at the terminal can be obtained by using an alkoxyamine compound having a functional group such as a hydroxyl group as described above. When this is used in the present invention, a polymer having a functional group at the terminal can be obtained.

There are no particular limitations on the polymerization conditions such as the monomer, solvent, polymerization temperature and the like used in the polymerization using a radical scavenger such as the nitroxide compound, but they may be the same as those used for the atom transfer radical polymerization described below.

Next, a more preferred atom transfer radical polymerization method will be described as the living radical polymerization method used in the present invention. In this atom transfer radical polymerization method, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having halogen at the α-position or a compound having halogen at the benzyl-position), or halogen Sulfonyl compounds and the like are used as initiators.

Specifically, C ₆ H ₅ —CH ₂ X, C ₆ H ₅ —C (H) (X) CH ₃ , C ₆ H ₅ —C (X) (CH ₃ ) ₂ (wherein C ₆ H ₅ is a phenyl group, X is a chlorine atom, a bromine atom or an iodine atom), R ¹ —C (H) (X) —CO ₂ R ² , R ¹ —C (CH ₃ ) (X) —CO ₂ ^{R 2, R 1 -C (H} ) (X) -C (O) R 2, R 1 -C (CH 3) (X) -C (O) R 2
Wherein R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, X is a chlorine atom, bromine atom or iodine atom )
R ³ —C ₆ H ₄ —SO ₂ X
(Wherein R ³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, X is a chlorine atom, bromine atom or iodine atom)
Etc.

As an initiator of the atom transfer radical polymerization method, an organic halide or a sulfonyl halide compound having a functional group other than the functional group for initiating polymerization can also be used. In such a case, a vinyl polymer having a structure represented by the general formula (1) at the end of one main chain and the functional group at the other main chain end is produced.

Examples of the functional group include an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group, and an amide group.

The organic halide having an alkenyl group is not particularly limited. For example, the general formula (4):
^{R 6 R 7 C (X)} -R 8 -R 9 -C (R 5) = CH 2 (4)
(In the formula, R ⁵ is a hydrogen atom or a methyl group, R ⁶ and R ⁷ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or others. Connected to each other at the ends, R ⁸ is —C (O) O— (ester group), —C (O) — (keto group), or o-, m-, p-phenylene group, R ⁹ is directly A divalent organic group having 1 to 20 carbon atoms which may contain a bond or one or more ether bonds, X is a chlorine atom, a bromine atom or an iodine atom)
What is shown by is illustrated.

Specific examples of the substituents R ⁶ and R ⁷ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. R ⁶ and R ⁷ may be linked at the other end to form a cyclic skeleton.

Examples of the divalent organic group having 1 to 20 carbon atoms that may contain one or more ether bonds of R ⁹ include, for example, 1 to 20 carbon atoms that may contain one or more ether bonds. Examples include an alkylene group.

Specific examples of the organic halide having an alkenyl group represented by the general formula (4) include
_{XCH 2 C (O) O (} CH 2) n CH = CH 2,
H ₃ CC (H) (X) C (O) O (CH ₂ ) _n CH═CH ₂ ,
(H ₃ C) ₂ C (X) C (O) O (CH ₂ ) _n CH═CH ₂ ,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n CH = CH 2

(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m CH = CH 2,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m CH = CH 2,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m CH = CH 2,
CH ₃ CH ₂ C (H) (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m CH═CH ₂

(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -O- (CH 2) m CH = CH 2
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1 to 20, and m is an integer of 0 to 20)
Etc.

The organic halide having an alkenyl group is further represented by the general formula (5):
_{^{H 2 C = C (R 5}} ) -R 9 -C (R 6) (X) -R 10 -R 7 (5)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ , X are the same as above, R ¹⁰ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group) ) Or o-, m-, p-phenylene group)
And the like.

R ⁹ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds). When it is a direct bond, R ⁹ is bonded to a halogen atom. A vinyl group is bonded to carbon, which is an allyl halide. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, it is not always necessary to have a C (O) O group or a phenylene group as R ¹⁰ , and a direct bond may be used. When R ⁹ is not a direct bond, R ¹⁰ is preferably a C (O) O group, a C (O) group, or a phenylene group in order to activate the carbon-halogen bond.

If the compound represented by the general formula (5) is specifically exemplified,
_{CH 2 = CHCH 2 X, CH} 2 = C (CH 3) CH 2 X,
_{CH 2 = CHC (H) (} X) CH 3, CH 2 = C (CH 3) C (H) (X) CH 3,
_{CH 2 = CHC (X) (} CH 3) 2, CH 2 = CHC (H) (X) C 2 H 5,
_{CH 2 = CHC (H) (} X) CH (CH 3) 2,
_{CH 2 = CHC (H) (} X) C 6 H 5, CH 2 = CHC (H) (X) CH 2 C 6 H 5,
_{CH 2 = CHCH 2 C (H} ) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 2 C (H) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 3 C (H) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 8 C (H) (X) -CO 2 R,
_{CH 2 = CHCH 2 C (H} ) (X) -C 6 H 5,
_{CH 2 = CH (CH 2)} 2 C (H) (X) -C 6 H 5,
_{CH 2 = CH (CH 2)} 3 C (H) (X) -C 6 H 5
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, R is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group)
Etc.

Specific examples of the sulfonyl halide compound having the alkenyl group include
_{o-, m-, p-CH 2} = CH- (CH 2) n -C 6 H 4 -SO 2 X,
_{o-, m-, p-CH 2} = CH- (CH 2) n -O-C 6 H 4 -SO 2 X
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20)
Etc.

The organic halide having a crosslinkable silyl group is not particularly limited. For example, the general formula (6):
^{R 6 R 7 C (X)} -R 8 -R 9 -C (H) (R 5) CH 2 - [Si (R 11) 2-b (Y) b O] m -Si (R 12) 3- _a (Y) _a (6)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are the same as above, R ¹¹ and R ¹² are all alkyl groups having 1 to 20 carbon atoms, aryl groups, aralkyl groups, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). An organosiloxy group, when two or more R ¹¹ or R ¹² are present, they may be the same or different; Y represents a hydroxyl group or a hydrolyzable group; and Y is two or more When present, they may be the same or different, a is 0, 1, 2 or 3, b is 0, 1 or 2, m is an integer from 0 to 19, provided that a + mb ≧ 1 Satisfied to be)
The following are exemplified.

If the compound represented by the general formula (6) is specifically exemplified,
XCH ₂ C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ ,
_{CH 3 C (H) (X} ) C (O) O (CH 2) n Si (OCH 3) 3,
(CH ₃ ) ₂ C (X) C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ ,
_{XCH 2 C (O) O (} CH 2) n Si (CH 3) (OCH 3) 2,
_{CH 3 C (H) (X} ) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2,
_{(CH 3) 2 C (X} ) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (OCH 3) 3,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (CH 3) (OCH 3) 2,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 3 -Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 -Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 2-O- (CH 2) 3Si (OCH 3) 3
(In the above formula, X is a chlorine atom, a bromine atom or an iodine atom)
Etc.

The organic halide having a crosslinkable silyl group is further represented by the general formula (7):
_{^{(R 12) 3-a (}} Y) a Si- [OSi (R 11) 2-b (Y) b] m -CH 2 -C (H) (R 5) -R 9 -C (R 6) ( X) -R ¹⁰ -R ⁷ (7)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , a, b, X, Y are the same as above, m is an integer of 0-19)
What is shown by is illustrated.

If the compound represented by the general formula (7) is specifically exemplified,
_{(CH 3 O) 3 SiCH 2} CH 2 C (H) (X) C 6 H 5,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C (H) (X) C 6 H 5,
_{(CH 3 O) 3 Si (} CH 2) 2 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 2 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 3 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 9 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 9 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -C 6 H 5,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 3 C (H) (X) -C 6 H 5,
_{(CH 3 O) 3 Si (} CH 2) 4 C (H) (X) -C 6 H 5,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 4 C (H) (X) -C 6 H 5
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, R is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group)
Etc.

The organic halide or sulfonyl halide compound having a hydroxyl group is not particularly limited, and examples thereof include the following.
_{HO- (CH 2) n -OC (} O) C (H) (R) (X)
(Wherein X is a chlorine atom, bromine atom or iodine atom, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
There is no limitation in particular in the organic halide or sulfonyl halide compound which has the said amino group, The following are illustrated.
_{H 2 N- (CH 2) n} -OC (O) C (H) (R) (X)
(Wherein X is a chlorine atom, bromine atom or iodine atom, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
There is no limitation in particular in the organic halide or halogenated sulfonyl compound which has the said epoxy group, The following are illustrated.

(Wherein X is a chlorine atom, bromine atom or iodine atom, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)

In order to obtain a vinyl polymer having two or more groups represented by the general formula (1) per molecule at the molecular end, an organic halide or sulfonyl halide compound having two or more starting points is used as an initiator. It is preferable to use as. For example,

Etc.

There is no restriction | limiting in particular in the vinyl-type monomer used in the said superposition | polymerization, and all already illustrated can be used suitably.

Further, the transition metal complex used as the polymerization catalyst is not particularly limited, but preferably a metal complex having a group 7 element, group 8, group 9, group 10 or group 11 element as a central metal, such as copper, It is a complex of nickel, ruthenium and iron. Further preferred are a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel. Of these, a copper complex is preferable.

Specific examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate and the like. Can be given.

In the case of using a copper compound, 2,2′-bipyridyl, its derivative, 1,10-phenanthroline, its derivative, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. to increase the catalytic activity A ligand such as a polyamine can be added.

A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst.

When a ruthenium compound is used as a catalyst, aluminum alkoxides can be added as an activator.

Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistributylphosphine complex ( NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

The polymerization can be carried out without solvent or in various solvents.

Solvent types include hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Solvents, alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, nitrile solvents such as acetonitrile, propionitrile, benzonitrile, ester solvents such as ethyl acetate, butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate. These may be used alone or in combination of two or more.

Moreover, superposition | polymerization can be performed in room temperature-200 degreeC, Preferably it is 50-150 degreeC.

<Functional group introduction method>
There are no particular limitations on the method for producing the component (A) and the component (C). For example, a vinyl polymer having a reactive functional group is produced by the aforementioned method, and the reactive functional group is converted to a (meth) acryloyl group. It can manufacture by converting into the substituent which has.

Below, the method to convert the terminal of the vinyl polymer which has a reactive functional group into group represented by General formula (1) is demonstrated.

The method for introducing the (meth) acryloyl group at the terminal of the vinyl polymer is not particularly limited, and examples thereof include the following methods.

(Introduction method 1)
A vinyl polymer having a halogen group at the terminal, and the general formula (8):
M ^{+ −} OC (O) C (R ^d ) ═CH ₂ (8)
(Wherein R ^d represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The method by reaction with the compound shown by these.

As the vinyl polymer having a halogen group at the terminal, the general formula (9):
-CR ¹³ R ¹⁴ X (9)
(In the formula, R ¹³ and R ¹⁴ are groups bonded to the ethylenically unsaturated group of the vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom)
Those having a terminal group represented by are preferred.

(Introduction method 2)
A vinyl polymer having a hydroxyl group at the terminal, and the general formula (10):
X ¹ C (O) C (R ^d ) ═CH ₂ (10)
(Wherein R ^d represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group)
The method by reaction with the compound shown by these.

(Introduction method 3)
A vinyl polymer having a hydroxyl group at the terminal is reacted with a diisocyanate compound to form a residual isocyanate group and the general formula (11):
HO—R′—OC (O) C (R ^d ) ═CH ₂ (11)
(Wherein R ^d represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ′ represents a divalent organic group having 2 to 20 carbon atoms)
The method by reaction with the compound shown by these.

Below, each said method is demonstrated in detail.

[Introduction method 1]
The introduction method 1 is a method by a reaction between a vinyl polymer having a halogen group at the terminal and a compound represented by the general formula (8).

Although there is no limitation in particular in the vinyl polymer which has a halogen group at the terminal, What has a terminal group shown in General formula (9) is preferable.

A vinyl polymer having a halogen group at the terminal, particularly a vinyl polymer having a terminal group represented by the general formula (9), is prepared by using the above-described organic halide or sulfonyl halide compound as an initiator and catalyzing a transition metal complex. Is produced by a method of polymerizing a vinyl monomer or a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, but the former is preferred.

There is no limitation in particular in the compound represented by General formula (8).

Examples of the organic group having 1 to 20 carbon atoms for R ^d in the general formula (8) are the same as those described above, and specific examples thereof are also the same as those described above.

M ⁺ in the general formula (8) is a counter cation of an oxyanion, and examples thereof include alkali metal ions and quaternary ammonium ions.

Examples of the alkali metal ion include lithium ion, sodium ion, and potassium ion. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, and tetrabutyl. Examples thereof include ammonium ion and dimethylpiperidinium ion. Of these, alkali metal ions are preferable, and sodium ions and potassium ions are more preferable.

The usage-amount of the compound shown by General formula (8) becomes like this. Preferably it is 1-5 equivalent with respect to the terminal group shown by General formula (9), More preferably, it is 1.0-1.2 equivalent.

The solvent for carrying out the reaction is not particularly limited, but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric trimethyl. Amides, acetonitrile and the like are preferably used.

Although there is no limitation in particular in reaction temperature, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.

[Introduction method 2]
The introduction method 2 is a method by a reaction between a vinyl polymer having a hydroxyl group at the terminal and a compound represented by the general formula (10).

There is no limitation in particular in the compound represented by General formula (10).

Examples of the organic group having 1 to 20 carbon atoms in R ^d in the general formula (10) are the same as those described above, and specific examples thereof are also the same as those described above.

The vinyl polymer having a hydroxyl group at the terminal is a method of polymerizing a vinyl monomer using the above-mentioned organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a compound having a hydroxyl group as a chain transfer agent. Although it is produced by a method of polymerizing a vinyl monomer, the former is preferred.

Although there is no limitation in particular in the method of manufacturing the vinyl polymer which has a hydroxyl group at the terminal, For example, the following methods are illustrated.

(A) When synthesizing a vinyl polymer by living radical polymerization, the general formula (12):
_{^{H 2 C = C (R 15}} ) -R 16 -R 17 -OH (12)
Wherein R ¹⁵ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ¹⁶ is —C (O) O— (ester group) or o-, m- or p-phenylene group, and R ¹⁷ is a direct bond. Or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds)
A method of reacting a compound having a polymerizable alkenyl group and a hydroxyl group in one molecule as a second monomer.

R ¹⁵ is preferably a hydrogen atom or a methyl group. Further, when R ¹⁶ is an ester group, it is a (meth) acrylate compound, and when R ¹⁶ is a phenylene group, it is a styrene compound.

There is no restriction on the timing for reacting a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule, but the end of the polymerization reaction or the completion of the reaction of a predetermined monomer is particularly desired when rubber-like properties are expected. Later, it is preferable to react as the second monomer.

(B) When synthesizing a vinyl polymer by living radical polymerization, the second monomer has a low polymerizable alkenyl group and hydroxyl group as the second monomer after the end of the polymerization reaction or after completion of the reaction of the predetermined monomer. A method of reacting a compound.

Although there is no limitation in particular in such a compound, For example, General formula (13):
_{^{H 2 C = C (R 15}} ) -R 18 -OH (13)
(In the formula, R ¹³ is the same as above, and R ¹⁸ represents a C 1-20 divalent organic group optionally having one or more ether bonds)
And the like.

The compound represented by the general formula (13) is not particularly limited, but alkenyl alcohols such as 10-undecenol, 5-hexenol and allyl alcohol are preferable because they are easily available.

(C) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (9) obtained by atom transfer radical polymerization by a method as disclosed in JP-A-4-132706. A method of introducing a hydroxyl group at a terminal by hydrolyzing or reacting a halogen atom with a hydroxyl group-containing compound.

(D) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (9) obtained by atom transfer radical polymerization is added to the general formula (14):
^{M + C - (R 19)} (R 20) -R 18 -OH (14)
(In the formula, R ¹⁸ and M ⁺ are the same as above, R ¹⁹ and R ²⁰ are both electron-withdrawing groups that stabilize carbanion C ⁻ or one is the electron-withdrawing group, the other is a hydrogen atom, and 1 to 10 carbon atoms. Represents an alkyl group or a phenyl group of
A method of replacing halogen by reacting a stabilized carbanion having a hydroxyl group represented by

Examples of the electron withdrawing group include —CO ₂ R (ester group), —C (O) R (keto group), —CON (R ₂ ) (amide group), —COSR (thioester group), —CN (nitrile group). ), —NO ₂ (nitro group) and the like, and —CO ₂ R, —C (O) R, and —CN are particularly preferable. The substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group.

(E) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (9) obtained by atom transfer radical polymerization is allowed to react with a metal simple substance or an organometallic compound such as zinc to enolate. A method in which an anion is prepared and then an aldehyde or a ketone is reacted.

(F) A vinyl polymer having at least one halogen atom represented by the general formula (9), preferably a halogen atom at the terminal of the polymer, is represented by the general formula (15):
HO-R ¹⁸ -O ^- M ⁺ (15)
(Wherein R ¹⁸ and M ⁺ are the same as above)
A hydroxyl group-containing compound represented by
Formula (16):
HO—R ¹⁸ —C (O) O ⁻ M ⁺ (16)
(Wherein R ¹⁸ and M ⁺ are the same as above)
A method in which the halogen atom is substituted with a hydroxyl group-containing substituent by reacting the hydroxyl group-containing compound represented by formula (1).

In the case where a halogen atom is not directly involved in the method of introducing a hydroxyl group as in (a) to (b), the method of (b) is more preferred because control is easier.

In addition, when a hydroxyl group is introduced by converting a halogen atom of a vinyl polymer having at least one carbon-halogen bond such as (c) to (f), control is easier (f). The method is more preferable.

The usage-amount of the compound shown by General formula (4) becomes like this. Preferably it is 1-10 equivalent with respect to the terminal hydroxyl group of a vinyl type polymer, More preferably, it is 1-5 equivalent.

The solvent for carrying out the reaction is not particularly limited, but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric trimethyl. Amides, acetonitrile and the like are preferably used.

Although there is no limitation in particular in reaction temperature, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.

[Introduction method 3]
In the introduction method 3, a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at the terminal, and the residual isocyanate group and the general formula (11):
HO—R′—OC (O) C (R ^d ) ═CH ₂ (11)
(Wherein R ^d represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ′ represents a divalent organic group having 2 to 20 carbon atoms)
It is the method by reaction with the compound shown by.

Examples of the organic group having 1 to 20 carbon atoms for R ^d in the general formula (11) are the same as those described above, and specific examples thereof are also the same as those described above.

Examples of the divalent organic group having 2 to 20 carbon atoms represented by R ′ in the general formula (5) include an alkylene group having 2 to 20 carbon atoms (ethylene group, propylene group, butylene group, etc.), and 6 to 20 carbon atoms. And alkylene groups having 7 to 20 carbon atoms.

The compound represented by the general formula (5) is not particularly limited, and particularly preferable compounds include 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and the like.

The vinyl polymer having a hydroxyl group at the terminal is as described above.

There is no particular limitation on the diisocyanate compound, and any conventionally known one can be used. Specific examples include toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogen. Examples thereof include xylylene diisocyanate and isophorone diisocyanate. These may be used alone or in combination of two or more. Moreover, you may use block isocyanate. From the viewpoint of obtaining superior weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring, such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate.

The amount of the diisocyanate compound used is preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents, relative to the terminal hydroxyl group of the vinyl polymer.

The reaction solvent is not particularly limited, but an aprotic solvent is preferred.

Although there is no limitation in particular in reaction temperature, Preferably it is 0-250 degreeC, More preferably, it is 20-200 degreeC.

The usage-amount of the compound shown by General formula (5) becomes like this. Preferably it is 1-10 equivalent with respect to a residual isocyanate group, More preferably, it is 1-5 equivalent.

<(B) component>
The component (B) has at least one aliphatic branched structure and alicyclic aliphatic structure in the molecule, and the general formula (2):
—OC (O) C (R ^b ) ═CH ₂ (2)
(Wherein R ^b represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
A compound having at least one group represented by the formula: For R ^b, same as the ^{R a} can be exemplified. The number of aliphatic branched structures is preferably 6 or less, the number of alicyclic aliphatic structures is preferably 5 or less, and the number of (meth) acryloyl groups is preferably 2 or less.

The aliphatic branched structure is not particularly limited, but i-propyl group, i-butyl group, t-butyl group, isoheptyl group, 2-ethylhexyl group, i-nonyl group, i-decyl group, An i-undecyl group, an i-dodecyl group and the like can be mentioned, and a t-butyl group is preferable from the viewpoint of the viscosity of the adhesive composition, the adhesiveness to the substrate, and the strength of the adhesive layer.

Examples of the alicyclic aliphatic structure include a cycloalkyl ring, a bicycloalkyl ring, a tricycloalkyl ring, a cycloalkenyl ring, a bicycloalkenyl ring, a tricycloalkenyl ring, and an adamantyl ring. More specifically, cyclopropyl ring, cyclobutyl ring, cyclopentyl ring, cyclohexyl ring, cycloheptyl ring, cyclooctyl ring, cyclononyl ring, cyclodecanyl ring, decahydronaphthyl ring, norbornyl ring, isobornyl ring, adamantyl ring, diamantyl ring, A cyclopentadienyl ring, a dicyclopentenyl ring, a dicyclopentanyl ring, etc. are mentioned. Of these, a cyclohexyl ring is preferable.

The group represented by the general formula (2) can be directly bonded to an alicyclic aliphatic group, or can be bonded via an alkylene group or an alkyloxylene group. As the preferred component (B), 4-isopropylcyclohexyl (meth) acrylate, 4-isopentyl (meth) acrylate, 4- (2-ethylhexyl)-(meth) acrylate, 4-isononyl (meth) acrylate, 4- Isodecyl (meth) acrylate, 4-isoundecyl (meth) acrylate, 4-isododecyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, 2,4 di (t-butyl)-(meth) acrylate, 2, Examples include 4,6 tri (t-butyl)-(meth) acrylate.

In the composition of the present invention, the component (B) may be used alone or in combination of two or more.

The amount of component (B) added is preferably 1 to 500 parts, more preferably 2 to 300 parts, and more preferably 3 to 200 parts, based on 100 parts of component (A) or (A) and component (C). Is particularly preferred.

As the dilution monomer, in addition to the component (B), another dilution monomer different from the component (B) can be used in combination. Examples of other dilution monomers include dicyclopentenyloxyethyl methacrylate, isobornyl acrylate, dicyclopentenyloxyethyl methacrylate, acryloyl morpholine, 2-hydroxyethyl methacrylate, (2-hydroxyethyl) methacrylate acid phosphate, dimethylacrylamide, and the like. Can be mentioned.

As a dilution monomer, in addition to the component (B), when another dilution monomer different from the component (B) is used in combination, the lower limit of the content of the component (B) in all the dilution monomers may be 10% by weight or more. Preferably, it is 20% by weight or more. Although an upper limit is not specifically limited, It is preferable that it is 90 weight% or less, and it is more preferable that it is 80 weight% or less. If it is less than 10% by weight, the adhesion to a hardly-adhesive substrate is insufficient, and if it exceeds 80% by weight, the cured product tends to be hard and peeling from the substrate tends to occur.

<(D) component>
Although there is no restriction | limiting in particular about the polymerization initiator of (D) component, A photoradical polymerization initiator is especially preferable. For example, benzophenone, acetophenone, propiophenone, xanthol, fluorin, benzaldehyde, anthraquinone, camphorquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3- Bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-chloro-4-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, 2, 4-diethylthioxanthone, isopropylthioxanthone, benzoyl, benzoin methyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxyketone Lumpur, 2-chlorothioxanthone, etc. 2,4,6-trimethylbenzoyl phenyl phosphine oxide. Further, radical photopolymerization initiators are commercially available, and typical examples include Irgacure 651 (2,2-dimethoxy-1,2-diphenylethane-1-one), Irgacure 184 (1-hydroxy-cyclohexylphenyl). Ketone), Darocur 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one), Irgacure 2959 (1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1- Propan-1-one), Irgacure 127 (2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one), Darocur MBF (phenyl) Glyoxylic acid methyl ester), I rgacure 907 (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one), Irgacure 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane- 1-one), Irgacure 379 (2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-ylphenyl) butan-1-one), Irgacure 819 (bis (2,4,6) -Trimethylbenzoyl) phenylphosphine oxide), Darocur TPO (2,4,6-trimethylbenzoylphenylphosphine oxide) (above, manufactured by Ciba Specialty Chemicals), KAYACURE BMS ([4- (Tylphenylthio) phenyl] phenylmeta Non), KAY CURE 2-EAQ (ethyl anthraquinone) (manufactured by Nippon Kayaku), BIPE (benzoin isopropyl ether), BIBE (benzoin isobutyl ether), NBCA (10-butyl-2-chloroacridone) (manufactured by Kurokin Kasei) ESACURE KIP150 series (oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone} and mixtures thereof) (manufactured by Lamberti) and the like.

These initiators may be used alone or in combination of two or more.

(D) As addition amount of a component, 0.01-20 parts are preferable with respect to a total of 100 parts of (A) component or (A) component, and (C) component, and 0.02-10 parts are more preferable. .

<(E) component>
Although there is no limitation in particular as a filler of (E) component, For example, wood powder, pulp, cotton chip, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, white clay, dolomite Reinforcing fillers such as silicic anhydride, hydrous silicic acid, carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, alumina, bentonite, organic bentonite Fillers such as ferric oxide, iron powder, aluminum fine powder, flint powder, zinc oxide, activated zinc white, zinc dust, zinc carbonate and shirasu balloon; asbestos, glass fiber and glass filament, carbon fiber, Kevlar fiber And fibrous fillers such as polyethylene fiber. Of these fillers, silicic anhydride, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable. In addition, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon, etc. may be added. it can.

These fillers may be used alone or in combination of two or more.

(E) As addition amount of a component, 1-1000 parts are preferable with respect to a total of 100 parts of (A) component or (A) component, and (C) component, 2-800 parts are more preferable, 5-600 Part is particularly preferred.

<Composition>
Various additives may be added as optional components to the composition of the present invention in order to adjust physical properties. Examples of the additive include an anti-aging agent, a plasticizer, a solvent, and an adhesion improver.

As the anti-aging agent, conventionally known antioxidants, light stabilizers, and the like can be used. The anti-aging agent can also be used for polymerization control during polymerization, and can control physical properties. Various types of antioxidants are known, and are described in, for example, “Antioxidant Handbook” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242) published by CM Chemical Co., Ltd. Although various things are mention | raise | lifted, it is not necessarily limited to these. For example, thioethers such as MARK PEP-36 and MARK AO-23 (all manufactured by Adeka Gas Chemical Co., Ltd.), Irgafos 38, Irgafos 168, Irgafos P-EPQ (all manufactured by Nihon Ciba Specialty Chemicals), etc. Examples thereof include phosphorus-based antioxidants. Of these, hindered phenol compounds as shown below are preferred.

Specific examples of the hindered phenol compound include the following. 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono (or di or tri) (α methylbenzyl) phenol, 2,2′-methylenebis (4 ethyl-6-tert-butylphenol), 2,2'-methylenebis (4methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4 ' -Thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, triethylene glycol-bis- [3- (3-t- Butyl-5-methyl-4hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- 3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1, 3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-) t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trime Til-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, tris -(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-2,4-bis [(octylthio) methyl] o-cresol, N, N'-bis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-t-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2 -[2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxypheny L) Benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5 -Chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) -benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-condensate with polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivative, 2- (3 5-Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pen) Methyl-4-piperidyl), e.g., 2,4-di -t- butyl-3,5-di -t- butyl-4-hydroxybenzoate and the like. In terms of product names, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all above Also manufactured by Ouchi Shinsei Chemical Co., Ltd.), MARK AO-30, MARK AO-40, MARK AO-50, MARK KAO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO- 80, MARK AO-15, MARK AO-18, MARK 328, MARK AO-37 (all manufactured by Adeka Argus Chemical Co., Ltd.), IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-102 4, IRGANOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all manufactured by Ciba Specialty Chemicals, Japan), Sumitizer GA-80 (all of which are Sumitomo Chemical ( However, it is not limited to these. Furthermore, monoacrylate phenolic antioxidants having both acrylate groups and phenol groups, nitroxide compounds and the like can be mentioned. Examples of the monoacrylate phenol-based antioxidant include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (trade name Sumilizer GM), 2, Examples include 4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate (trade name: Sumilizer GS). Nitroxide compounds include, but are not limited to, cyclic hydroxyamines such as 2,2,6,6-substituted-1-piperidinyloxy radicals and 2,2,5,5-substituted-1-pyrrolidinyloxy radicals. The nitroxy free radicals from are illustrated. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable. Specific nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1- Piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1, Examples include 1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like. Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used. Antioxidants may be used in combination with light stabilizers, and are particularly preferred because they can further exert their effects and in particular improve the heat resistance. Tinuvin C353, Tinuvin B75 (all of which are manufactured by Nippon Ciba Specialty Chemicals) or the like in which an antioxidant and a light stabilizer are mixed in advance may be used.

Antiaging agents may be used alone or in combination of two or more.

The addition amount of the anti-aging agent is preferably 0.01 to 10 parts, more preferably 0.02 to 5 parts with respect to 100 parts in total of the component (A) or the components (A) and (C).

Examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate; dioctyl adipate, dioctyl sebacate, etc. Non-aromatic dibasic acid esters; esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphate esters such as tricresyl phosphate and tributyl phosphate; chlorinated paraffins; alkyl diphenyl, partial water Hydrocarbon oils such as added terphenyl can be used alone or in admixture of two or more, but this is not always necessary. These plasticizers can also be blended at the time of polymer production.

The solvent may be optionally used for the purpose of reducing the viscosity of the formulation and improving workability. As the solvent, those having a boiling point of 50 to 180 ° C. are usually preferable because of excellent workability during coating and drying before and after curing. Specifically, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, isobutanol; methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, etc. Ester solvents; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; and cyclic ether solvents such as dioxane. These solvents may be used alone or in combination of two or more.

Examples of the adhesion improver (adhesion imparting agent) include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropeno Alkyl isopropenoxy silane such as xy silane, γ-glycidoxy propyl methyl diisopropenoxy silane, γ-glycidoxy propyl methyl dimethoxy silane, γ-glycidoxy propyl trimethoxy silane, vinyl trimethoxy silane, vinyl dimethyl Methoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane γ-mercap Trimethoxysilane, alkoxysilanes having a functional group such as γ- mercaptopropyl methyldimethoxysilane; silicone varnishes; polysiloxanes, a phosphoric acid-based monomers such as (2-hydroxyethyl) methacrylate acid phosphate and the like.

The addition amount of the adhesion improver (adhesion imparting agent) is preferably 0.01 to 20 parts with respect to 100 parts in total of (A) component or (A) component and (C) component, 10 parts is more preferred.

<Curing method>
Although there is no limitation in particular about the hardening method of a composition, the method of hardening with an active energy ray is preferable. The active energy rays mentioned here refer to, for example, visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays, electron beams, and the like. From the viewpoint of obtaining a particularly good cured product, a curing method using ultraviolet rays or electron beams is more preferable.

In the case of curing with active energy rays, it is preferable that the composition contains a radical photopolymerization initiator (D) as necessary.

When a radical photopolymerization initiator is used, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, para-tertiary butyl catechol or the like can be added as necessary.

Moreover, you may use a near-infrared light absorptive cationic dye as a near-infrared photoinitiator.

Near-infrared light absorbing cationic dyes are excited by light energy in the region of 650 to 1500 nm, for example, near-infrared light disclosed in JP-A-3-111402, JP-A-5-194619, etc. It is preferable to use an absorbing cationic dye-borate anion complex or the like, and it is more preferable to use a boron sensitizer together.

There is no particular limitation on the source of active energy rays, but depending on the nature of the photopolymerization initiator, for example, high-pressure mercury lamp, low-pressure mercury lamp, electron beam irradiation device, halogen lamp, light-emitting diode, semiconductor laser, etc. Irradiation.

<Substrate>
The composition of the present invention is suitable when a difficult-to-adhere substrate that has been difficult to give strong adhesion with conventional adhesives is used as an adherend. Examples of the difficult-to-adhere substrate mentioned here include thermoplastic resins, glass, magnesium alloys, aluminum alloys, and the like.

Among thermoplastic resins, those called engineering plastics or super engineering plastics are often poor in adherence, so that the composition of the present invention can be used preferably. Examples of engineering plastics or super engineering plastics include polycarbonate (PC), polycycloolefin (COP), polyamide 6 (PA6), polyamide 66 (PA66), polyacetal (POM), modified polyphenylene ether (m-PPE), and polybutylene. Terephthalate (PBT), GF reinforced polyethylene terephthalate (GF-PET), ultra high molecular weight polyethylene (UHMW-PE), polysulfone (PSF), polyethersulfone (PES), polyphenylene sulfide (PPS), amorphous polyarylate ( PAR), polyamideimide (PAI), polyetherimide (PEI), polyetheretherketone (PEEK), liquid crystal polymer (LCP), thermoplastic polyimide (T I), polybenzimidazole (PBI), polymethylbenten (TPX), polycyclohexanedimethylene terephthalate (PCT), polyamide 46 (PA46), polyamide 6T (PA6T), polyamide 9T (PA9T), polyamide 11,12 (PA11) 12), polyamide MXD6 (MXD6), syndiotactic polystyrene (SPS) and the like.

Of these, PC, COP, PPS, LCP, PAR and the like are often poor in adherence, so that the composition of the present invention can be preferably used.

Examples of the glass include soda lime glass, crystal glass, quartz glass, and borosilicate glass.

Examples of magnesium alloys include AZ alloys containing aluminum and zinc as trace components, and LA alloys containing lithium and aluminum as trace components.

Examples of the aluminum alloy include duralumin.

<Application>
In recent years, the hardly-adhesive base material is often used for optical members described below from the viewpoints of heat resistance, lightness, transparency, and the like. Therefore, the adhesive composition of the present invention can be suitably used for bonding optical members. The adhesion of the optical member is, for example, bonding of the optical members, fixing adhesion of the optical member to another substrate, or the like. Examples of the optical member include a pickup lens used in a recording / reproducing apparatus for an optical disk such as a DVD or a BD and its peripheral material, a peripheral material for a recording / reproducing laser; a digital camera, a digital video camera, a projector, an image sensor, a mobile phone. And imaging device (CCD, CMOS) used in PHS, etc., flexible printed circuit board (FPC) around the lens, imaging device peripheral material; optical communication system (optical switch, optical connector, optical fiber, optical waveguide, light receiving) Various components used in devices, laser light sources, etc .; Light emitting diode (LED) chips; Backlights used in flat panel displays (FPD) and their peripheral materials, LEDs, FPCs; Peripheral materials for solid lasers and semiconductor lasers ( Lens, reflector, prism, light Filter, shutter, light receiving elements, wave plates, etc. polarizing plate) may be mentioned such. Peripheral materials here refer to materials that come into contact with lenses, lasers, elements, etc. and their housings.

In addition, in the recording / reproducing apparatus for optical disks such as DVD and BD, the above-mentioned difficult-to-adhere base material is often used not only for optical members but also for other members, and the adhesive composition of the present invention is preferably used. It is possible to use. Examples of members of a recording / reproducing apparatus for an optical disk that can use the adhesive composition of the present invention as an adhesive include a pickup optical system and its peripheral materials, specifically a pickup objective lens, a collimator lens, and a cylindrical lens. , Prisms, wave plates, light receiving elements, reflecting mirrors, pickup lens holders, lens fixing flanges, housings, etc .; actuator peripheral materials, specifically magnets, coils, yokes, resin parts for driving, housings, etc .; laser light sources Peripheral materials, specifically lenses, reflectors, prisms, optical filters, shutters, light receiving elements, wave plates, polarizing plates, etc .; hard disk drive (HDD) peripheral materials, specifically spindle motor members (magnets, coils) , Bearings, shafts, connectors, etc.), for magnetic head actuators Such as wood; also, like housing in general for these components and the like.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

In the following examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-804 and K-802.5; Showa Denko KK) and chloroform as a GPC solvent were used.

In the following examples, “average number of terminal (meth) acryloyl groups” is “number of (meth) acryloyl groups introduced per molecule of polymer”, and the number average molecular weight determined by ¹ H-NMR analysis and GPC. Calculated. However, ¹ H-NMR was measured at 23 ° C. using ASX-400 manufactured by Bruker and using deuterated chloroform as a solvent.

In the examples and comparative examples below, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

(Production Examples 1 and 2)
Table 1 shows the amount of each raw material used.

(1) Polymerization process Acrylic acid ester (premixed acrylic acid ester) was deoxygenated. The inside of the stainless steel reaction vessel equipped with a stirrer was deoxygenated, and cuprous bromide and a part of the total acrylic ester (described as the initial charge monomer in Table 1) were charged and stirred with heating. Acetonitrile (described as “Acetonitrile for polymerization” in Table 1), diethyl 2,5-dibromoadipate (DBAE) or ethyl 2-bromobutyrate as an initiator were added and mixed, and the temperature of the mixture was adjusted to about 80 ° C. Pentamethyldiethylenetriamine (hereinafter abbreviated as triamine) was added to initiate the polymerization reaction. The remaining acrylic ester (described as an additional monomer in Table 1) was added sequentially to proceed the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during the polymerization is shown in Table 1 as a triamine for polymerization. As the polymerization proceeds, the internal temperature rises due to the heat of polymerization, so the polymerization was allowed to proceed while adjusting the internal temperature to about 80 ° C to about 90 ° C.

(2) Oxygen treatment step When the monomer conversion rate (polymerization reaction rate) was about 95% or more, an oxygen-nitrogen mixed gas was introduced into the gas phase part of the reaction vessel. While maintaining the internal temperature at about 80 ° C. to about 90 ° C., the reaction solution was heated and stirred for several hours to bring the polymerization catalyst in the reaction solution into contact with oxygen. Acetonitrile and unreacted monomer were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer. The concentrate was markedly colored.

(3) First crudely purified butyl acetate was used as a diluent solvent for the polymer. The concentrate of (2) is diluted with about 100 to 150 kg of butyl acetate with respect to 100 kg of the polymer, and a filter aid (Radiolite R900, manufactured by Showa Chemical Industry Co., Ltd.) and / or an adsorbent (Kyoword 700 SEN, Kyoward 500 SH) ) Was added. After introducing an oxygen-nitrogen mixed gas into the gas phase part of the reaction vessel, the mixture was heated and stirred at about 80 ° C. for several hours. Insoluble catalyst components were removed by filtration. The filtrate was colored and slightly turbid due to the polymerization catalyst residue.

(4) The second crude purified filtrate was charged into a stainless steel reaction vessel equipped with a stirrer, and adsorbents (Kyoward 700SEN, Kyoward 500SH) were added. After introducing an oxygen-nitrogen mixed gas into the gas phase and heating and stirring at about 100 ° C. for several hours, insoluble components such as an adsorbent were removed by filtration. The filtrate was almost clear and clear. The filtrate was concentrated to obtain an almost colorless and transparent polymer.

(5) (Meth) acryloyl group introduction step 100 kg of polymer is dissolved in about 100 kg of N, N-dimethylacetamide (DMAC), and potassium acrylate (in Production Example 1, about 2 molar equivalents relative to the terminal Br group, In Production Example 2, about 1 molar equivalent based on the terminal Br group), heat stabilizer (H-TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl), adsorbent ( Kyoward 700SEN) was added and stirred at about 70 ° C. for several hours. DMAC was distilled off under reduced pressure, the polymer concentrate was diluted with about 100 kg of toluene with respect to 100 kg of the polymer, a filter aid was added, the solid content was filtered off, the filtrate was concentrated, and an acryloyl group was added to the end. Polymers [P1] and [P2] having Table 1 shows the number of acryloyl groups introduced per molecule of the obtained polymer, the number average molecular weight, and the molecular weight distribution.

Example 1
The polymer [P1] 34.0 parts obtained in Production Example 1 as the component (A), 22.6 parts of the component [P2] as the component (C), and t-butylcyclohexyl methacrylate (trade name TBCHMA as the component (B) Manufactured by Nippon Oil and Fats Co., Ltd. 22.6 parts, and other acrylic monomers as isobornyl acrylate (trade name; IBXA, manufactured by Kyoeisha Chemical Co., Ltd.) 11.3 parts, 2-hydroxyethyl methacrylate (trade name, HO-250 manufactured by Kyoeisha Chemical Co., Ltd.) 3.8 parts, (2-hydroxyethyl) methacrylate acid phosphate (trade name: JPA514, manufactured by Johoku Chemical Co., Ltd.) 1.0 part as an adhesion-imparting component, 2-hydroxy-1--1- {4- [4 -(2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (trade name IRGACURE127 Ciba Japan) 3.8 parts, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name; IRGACURE 819, Ciba Japan) 0.5 parts, fine particle silica as thixotropic component (Product name: ASEROSIL ^# 200, manufactured by Nippon Aerosil Co., Ltd.) 0.25 parts, dimethylacrylamide (trade name DMAA; manufactured by Kojin Co., Ltd.) is added, 0.25 is added, and 2 hours with a 2 L planetary mixer (manufactured by Inoue Seisakusho) Kneaded. Then, 60 parts of spherical silica having an average particle diameter of 1.3 to 2.0 μm (trade name; SOC5, manufactured by Admatech) as a component (E), spherical silica having an average particle diameter of 6 μm (trade name; FB301, manufactured by Denki Kagaku Kogyo) 180 parts were added and kneaded with the mixer for 16 hours to obtain a curable composition for adhesives. The formulation of the adhesive composition is shown in Table 2. After measuring the viscosity of the obtained adhesive composition at 23 ° C., it was poured into a cylindrical mold and UV-cured with an integrated light amount of 6000 mJ / cm ² . Using this cured product, DuroD hardness and cure shrinkage were measured. Further, a shear sample of polycarbonate and each substrate was prepared by UV curing under irradiation conditions of 6000 mJ / cm ² and the strength was measured. The results are shown in Tables 2 and 3.

Each measurement condition is shown below.

<Viscosity measurement>
Under the condition of 23 ° C., the BH type viscosity, No. The viscosity at 2 rpm and 20 rpm was measured using 7 rotors.

<DuroD hardness>
In accordance with JIS K 6254, the hardness of the cured adhesive was measured.

<Curing shrinkage>
Curing shrinkage was calculated by the following formula.
(Cured product specific gravity-liquid specific gravity of adhesive before curing) / cured product specific gravity * 100

<Shear strength>
The measurement was performed according to JIS K 6850.

(Examples 2-7, Comparative Examples 1-5)
In the same manner as in Example 1, adhesive compositions having the formulations shown in Tables 2 and 3 were prepared, and the above physical properties were measured. The results are shown in Tables 4 and 5.

As shown in Tables 4 and 5, the vinyl polymer (A) component and / or the adhesive using the component (C) and the component (B) shown in the claims are monomers other than the component (B). Compared to the case where is used, better substrate adhesion and cure shrinkage are shown.

The adhesive composition for difficult-to-adhere base materials of the present invention can be obtained by adding a vinyl monomer having a specific alicyclic aliphatic structure and an initiator to a vinyl polymer, and a filler as necessary. Adhesiveness with respect to a substrate that has been difficult to bond is improved, and is suitable for use as an adhesive for optical members.

Claims (10)

(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
The a group represented by possess two or more per molecule, and a group represented by the general formula (1) Yes 1 or more at the molecular ends (meth) reactive oligomer comprising an acrylic polymer,
(B) having at least one aliphatic branched structure and alicyclic aliphatic structure in the molecule,
And general formula (2):
—OC (O) C (R ^b ) ═CH ₂ (2)
(Wherein R ^b represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
A diluent monomer having one or more groups represented by formula (1) at the molecular end, and (C) general formula (3):
—OC (O) C (R ^c ) ═CH ₂ (3)
(Wherein R ^c represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
The vinyl group monomer constituting the main chain includes the same as the vinyl monomer constituting the main chain of the component (A) (meth) Acrylic polymer,
Is an adhesive composition for difficult-to-adhere base materials containing as an essential component,
The aliphatic branched structure is i-propyl group, i-butyl group, t-butyl group, isoheptyl group, 2-ethylhexyl group, i-nonyl group, i-decyl group, i-undecyl group, or i-dodecyl group,
The alicyclic aliphatic structure is a cycloalkyl ring, a bicycloalkyl ring, a tricycloalkyl ring, a cycloalkenyl ring, a bicycloalkenyl ring, a tricycloalkenyl ring, or an adamantyl ring,
(C) Content of a component is 10-100 weight part with respect to 100 weight part of (A) component,
(B) Content of a component is 2-300 weight part with respect to a total of 100 weight part of (A) component and (C) component,
Difficult-to-bond substrates, polyphenylene sulfide, polycycloolefin, Ru crystal polymer or a magnesium alloy der, difficult-to-bond substrates for adhesive compositions. The adhesive composition for difficult-to-adhere base materials according to claim 1, wherein the aliphatic branched structure of component (B) is a t-butyl group. The adhesive composition for difficult-to-adhere base materials according to claim 1 or 2 , further comprising (D) a polymerization initiator. (D) Component is a radical photopolymerization initiator, The adhesive composition for hard-to-adhere base materials according to claim 3 characterized by things. The adhesive composition for difficult-to-adhere base materials according to any one of claims 1 to 4 , wherein the molecular weight distribution of the component (A) and / or the component (C) is less than 1.8. Furthermore, (E) Filler is contained, The adhesive composition for hard-to-adhere base materials in any one of Claims 1-5 characterized by the above-mentioned. The adhesive agent which used the adhesive composition for hard-to-adhere base materials in any one of Claims 1-6 as a main component. The adhesive according to claim 7 , wherein the adhesive is used for bonding an optical member. The adhesive according to claim 7 or 8 , wherein the adhesive is used for manufacturing an optical disk device. An optical disc device manufactured using the adhesive according to any one of claims 7 to 9 .