KR20140045915A - Actinic radiation curable resin composition containing polyfunctional acrylate compound - Google Patents

Abstract

The present invention is an adhesive for fixing a part including metal or plastic with high precision, has high initial adhesiveness to the member, shows high holding force in durability test including high temperature and high humidity test, The deformation | transformation with respect to a load is suppressed very little, and therefore the resin composition which can suppress the movement of a component is provided. As the active energy ray-curable resin composition of the present invention, the following components (A) to (D): (A) (a1) A linear or branched multimer thereof having a glycerol derivative and an ether skeleton as a linking functional group, (a2 A) linear or branched multimer thereof having a trimethylolpropane derivative and an ether skeleton as a linking functional group, (a3) linear or branched multimer thereof having the monomer and ether skeleton of a pentaerythritol derivative as a linking functional group and (a4) Contains an ether bond or an ester bond, and contains four or more (meth) acryloyl groups in a molecule selected from the group consisting of a tree molecular compound having a (meth) acryloyl group disposed at four or more terminals thereof. It contains a functional acrylate compound, (B) photocurable prepolymer, (C) monofunctional or bifunctional (meth) acryloyl group containing monomer, and (D) photoinitiator. Provided is an active energy ray curable resin composition.

Description

Active energy ray curable resin composition containing polyfunctional acrylate compound {ACTINIC RADIATION CURABLE RESIN COMPOSITION CONTAINING POLYFUNCTIONAL ACRYLATE COMPOUND}

The present invention provides adhesiveness to an active energy ray-curable resin composition including a multifunctional acrylate compound, particularly a metal or plastic member, and provides high retention and thermal dimensional stability in durability tests including heat resistance tests. It is related with the active energy ray curable resin composition hardened | cured by irradiation of active energy rays, such as UV and visible light.

In the field of base materials used for recording and reproducing CDs or DVDs, or recently, recording materials including Blu-Ray, with the miniaturization of the device, each member is required to have high heat resistance and impact resistance, and thus high precision. Liquid crystal polymer (LCP), cycloolefin polymer (COP), cycloolefin copolymer (COC), polyphenylene sulfide (PPS), polyphenylene oxide (PPO), which can be molded, or glass fiber or carbon fiber The composite plastic material kneading | mixing was used a lot. In order to bond and fix parts containing these materials, an adhesive with high fixing accuracy, which has high adhesiveness and high durability to these materials and has little deformation at the time of heat of the resin portion after curing, is required. In addition, in view of workability, it is required to be an adhesive that cures more rapidly by irradiation of active energy rays such as visible light and ultraviolet light.

Fixed precision is the precision which shows that a light detector does not move at a predetermined position, when fixing a light emitting element or a light detector to the housing which is a base member containing said member. If the fixing accuracy is low, the light emitting element or the photodetector moves at a predetermined position during the manufacture of the optical pickup device or after the endurance test, and the light detection becomes impossible. Therefore, high fixing precision is required.

Considering the fixed accuracy, the photocurable adhesive is superior to the photocurable acrylic resin adhesive than the photocurable acrylic resin adhesive, and the cationic curable epoxy resin composition does not inhibit hardening by oxygen as in the acrylic resin adhesive (Non Patent Literature 1). . However, the cation-curable epoxy resin has a problem that the fast curing property is inferior to the acrylic resin system.

In patent document 1, the curable composition which can be used as an adhesive agent to adherends, such as a liquid crystal polymer, a cycloolefin polymer, a polyarylate, and a polycarbonate, is disclosed. In recent years, in acrylic adhesives, after fixing a member, the movement of the member due to the deformation of the resin regarding the thermal stress and external stress of the resin, especially during heat, has become a problem. The acrylic adhesive has the advantage that the curability is better than that of the epoxy resin, whereas the change in elastic modulus when heat is applied is large, so that the adhesive is deformed to allow movement of the member.

PTL 2 describes a polarizing plate including a polarizer, an adhesive layer and a cured resin layer. Patent Document 2 describes that a cured resin layer formed of a solvent-free photocurable composition containing at least one of a polyfunctional acrylic monomer and a polyfunctional methacryl monomer and a photocurable prepolymer is used as a hard coating (high hardness) layer. It is. However, when the non-solvent type photocurable composition of patent document 2 was used as an adhesive agent, there existed a problem that cure shrinkage was large and curling (bending) and peeling were easy to occur.

Japanese Patent Laid-Open No. 2008-101106 Japanese Patent Publication No. 2008-20891

"Photonics Technology and Materials Dictionary", 160 pages, published April 26, 2006

DISCLOSURE OF THE INVENTION Problems of the Invention The present invention has a high initial adhesiveness to a plastic material or a metal member such as polyphenylene sulfide (PPS), and exhibits a high holding force in durability tests including high temperature and high humidity tests, and thus its deformation at thermal time, heat time and load. It is an object of the present invention to provide a resin composition capable of suppressing very little deformability and thereby suppressing movement of parts.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, it discovered that the active energy ray curable composition containing the following (A) component-(D) component can achieve the said objective, The present invention has been reached.

That is, this invention is an active energy ray curable resin composition, Comprising: (A) component-(D) component:

(A) (a1) Glycerol derivatives and their multimers which are linear or branched form having an ether skeleton as a linking functional group,

(a2) trimethylolpropane derivatives and their multimers which are linear or branched with an ether skeleton as a linking functional group,

(a3) a multimer thereof which is linear or branched with the monomer and ether skeleton of a pentaerythritol derivative as a linking functional group, and

(a4) A tree-like molecular compound comprising an ether bond or an ester bond and having a (meth) acryloyl group disposed at four or more ends thereof.

A polyfunctional acrylate compound containing four or more (meth) acryloyl groups in a molecule, selected from the group consisting of

(B) photocurable prepolymer,

(C) a monofunctional or bifunctional (meth) acryloyl group-containing monomer and

(D) It contains the photoinitiator, It is related with the active energy ray curable resin composition.

This invention relates to the active energy ray curable resin composition as described above whose (A) component is 0.01-25 weight% with respect to the weight of (A) component-(D) component.

The present invention relates to the active energy ray-curable resin composition described above, which is an adhesive for bonding optical components.

The present invention relates to the active energy ray-curable resin composition described above, which is an adhesive for assembling an optical pickup device.

The present invention relates to an adhesive structure bonded with the active energy ray curable resin composition described above.

The present invention relates to an optical component bonded by using the active energy ray curable resin composition described above.

The present invention relates to an optical pickup device assembled using the active energy ray curable resin composition described above.

According to the present invention, it has a high initial adhesiveness to a plastic member or a metal member such as polyphenylene sulfide (PPS), exhibits a high holding force in the durability test including high temperature and high humidity test, so that The deformation | transformation with respect to very little is suppressed, and the resin composition which can suppress the movement of a component is obtained by this.

By this invention, when workability | operativity, such as syringe coating property, is favorable and irradiated with ultraviolet light, the active energy ray curable resin composition which can harden | cure in short time is provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an apparatus for measuring the deformation | transformation of the adhesive agent part at the time of the heat of the curable composition of this invention from an angle change.
FIG. 2: is a figure for measuring an angular change with a tilt sensor, after peeling a jig | tool after photocuring the curable composition of this invention.
FIG. 3: is a schematic diagram of the puncture strength test of the adhesive structure bonded by the active energy ray curable resin composition of this invention.

In the present invention, the component (A) is a linear or branched multimer having (a1) a glycerol derivative and an ether skeleton as a linking functional group, (a2) a linear form having a trimethylolpropane derivative and an ether skeleton as a linking functional group or A branched multimer thereof, (a3) a linear or branched multimer having a monomer and an ether skeleton of a pentaerythritol derivative as a linking functional group, and (a4) an ether bond or an ester bond, wherein the (meth) It is a polyfunctional acrylate compound containing four or more (meth) acryloyl groups in a molecule | numerator chosen from the group which consists of the tree-like molecular compound in which acryloyl group was arrange | positioned. (A) A component may be used independently, respectively, or may be used in combination of 2 or more type. In addition, in the present specification, (meth) acrylate includes both acrylate and methacrylate, and the (meth) acryloyl group includes both acryloyl group and methacryloyl group.

In the present invention, a glycerol derivative, a trimethylolpropane derivative, a pentaerythritol derivative and a linear or branched multimer thereof having an ether skeleton as a linking functional group include glycerol units, trimethylolpropane units and pentaerythritol units in the molecule. And four or more (meth) acryloyl groups in the molecule. The glycerol unit is a structure in which three hydroxy groups are removed from glycerol, and the trimethylolpropane unit is a structure in which three hydroxy groups are removed from trimethylolpropane, and the pentaerythritol unit is a structure in which four hydroxyl groups are removed from a pentaerythritol unit. to be.

In the present invention, glycerol derivatives, trimethylolpropane derivatives and pentaerythritol derivatives are compounds in which glycerol, trimethylolpropane and pentaerythritol are substituted with four or more (meth) acryloyl groups.

The ether skeleton, which is a linking functional group in the present invention, is an ether bond formed by condensation of two hydroxy groups between molecules of glycerol, trimethylolpropane and pentaerythritol, or is glycerol, trimethylolpropane or pentaerythritol, and ethylene glycol It is a polyether skeleton formed by condensation with dialcohol compounds, such as these. The ether skeleton which is a linking functional group in this invention is represented by following General formula (1).

(Wherein,

X is alkylene having 1 to 4 carbon atoms,

n1 is 0 or an integer from 1 to 3)

Examples of the alkylene having 1 to 4 carbon atoms include methylene, ethylene, trimethylene and tetramethylene, and preferably ethylene.

In the formula (1), n1 is preferably 0. That is, the ether skeleton in the present invention is preferably an ether bond (-O-).

In the present invention, the compound represented by the following general formula (2) is preferably a multimer of a linear glycerol derivative having an ether skeleton as a linking functional group.

(Wherein,

n2 is 2 to 10,

R ¹ is hydrogen, acryloyl or methacryloyl,

R ² is hydrogen or methyl,

However, the sum of acryloyl and methacryloyl is 4 or more)

In the present invention, as the multimer of the linear trimethylolpropane derivative having an ether skeleton as a linking functional group, a compound represented by the following general formula (3) is preferable.

(Wherein,

n2, R ¹ and R ² are as defined in formula (2),

However, the sum of acryloyl and methacryloyl is 4 or more)

In this invention, the compound represented by following General formula (4) is preferable as a multimer of the linear pentaerythritol derivative which has an ether skeleton as a linking functional group.

(Wherein,

n3 is 1 to 10,

R ¹ is as defined in formula (2),

However, the sum of acryloyl and methacryloyl is 4 or more)

In the present invention, a linear or branched multimer having an ether skeleton as a linking functional group is particularly preferably a compound represented by the general formula (5).

(Wherein,

R < ³ > is hydrogen or methyl,

n4 is 1 to 5,

However, the sum of acryloyl and methacryloyl is 4 or more)

In the compound represented by the formula (5), n4 is more preferably 3-4. By using such a compound, the deformation | transformation at the time of heat, and the resin composition in which the deformation property with respect to heat time and weight are very little suppressed can be provided.

As a commercial item, the compound represented by General formula (5) is V # 802 (n4 = 3.45 in Chemical formula (5)) (made by Osaka Yuki Chemical Co., Ltd.), DPE-6A (Dipentaerythritol hexaacrylate), and PE- 4A (Kyoeisha Chemical Co., Ltd. product) is mentioned.

In the present invention, a multifunctional acrylate compound multimerized into a branched phase having a branched structure by a linking functional group is a glycerol derivative, a trimethylolpropane derivative, and a pentaerythritol derivative having a large amount in the branched phase using an ether skeleton as a linking functional group. It is a compound embodied. Such a multimer is a compound which multimerized the structure which removed the hydroxyl group from glycerol, trimethylol propane, and pentaerythritol through the coupling functional group which is an ether skeleton, for example, and is a compound which has four or more (meth) acryloyl groups. For example, the structure of pentaerythritol which pentaerythritol derivative is contained in the polyfunctional acrylate compound branched multimerized via a linking functional group is represented by following General formula (6a)-(6d).

Wherein R ¹ is as defined above.

In the present invention, the compound which is a branched multimer of pentaerythritol derivative is a structure in which structures represented by the formulas (6a) to (6d) are bonded at random through an ether skeleton (however, represented by the formula (6b) A multimer branched in a straight line with only the structure, and branched in a straight line to which the structure represented by the formula (6a) is bonded at the end thereof). In the present invention, the compound which is a branched multimer of the pentaerythritol derivative bonded randomly may have any structure, for example, may be cyclic or may have a mesh-like structure.

As a branched multimer of a pentaerythritol derivative, the compound represented by General formula (7) is mentioned, for example. As such a branched multimer of pentaerythritol having an ether bond as a linking functional group, V # Star-501 (manufactured by Osaka Oil Chemical Industries, Ltd.) can be mentioned.

(Wherein,

n5 is 1 to 10,

n6 is 0 to 10,

R ¹ is as defined in formula (2),

R ² is of formula (8) or formula (9),

The sum of acryloyl and methacryloyl groups in one molecule is 4 or more)

(Wherein,

n7 is 1 to 10,

R ¹ is as defined in formula (2))

(Wherein,

R ¹ is as defined in formula (2),

n8 is 1 to 10,

n9 is 0 to 10,

R ⁴ is a group represented by formula (8)

Polyfunctional acrylate compound containing four or more (meth) acryloyl groups in a molecule | numerator which is an arbor molecular compound which contains an ether bond or an ester bond in this invention, and has a (meth) acryloyl group arrange | positioned at four or more terminals. Silver is a compound which has a chemical structure comprised from the resin structure containing a core and a branching unit. As such a compound, a dendrimer type acrylate compound is mentioned. In the tree-like molecular compound of the present invention, the first resin structure and its terminal portion from the core are defined as the first generation. When it has the next resin structure on the outer side of the resin structure of a 1st generation, from the said next resin structure to its terminal is defined as a 2nd generation. Like the third generation after the third generation, the next generation is defined as the next generation. As a preferable generation number in the dendrimer of this invention, it is the range of 1-5, More preferably, it is 1-3.

In the present invention, trimethylolpropane, pentaerythritol, and dipentaerythritol are mentioned as cores of the tree-like molecular compound.

In this invention, the structure represented by following General formula (10) is mentioned as a resin structure containing the branching unit of a tree molecular compound. Here, R <^1> in General formula (10) is corresponded to the terminal of the tree compound of this invention.

(Wherein,

R ¹ is as defined in formula (2),

s is an integer from 1 to 5)

The repeating number s in the formula (10) corresponds to the number of generations of the dendrimer compound. For example, when repeating number s in General formula (10) is 2, it is represented by following (10a).

(Wherein,

R ¹ is as defined in formula (2))

In the present invention, the compound represented by the following general formula (11) is preferably an arbor molecular compound including an ether bond or an ester bond and having a (meth) acryloyl group disposed at its terminal.

{Wherein,

n10 are each independently an integer of 1 to 3,

R ⁴ independently of one another is hydrogen, acryloyl, methacryloyl or formula (10),

Provided that the sum of acryloyl and methacryloyl is at least 4}

(Wherein,

R ¹ and s are as defined above)

In the present invention, a polyfunctional acrylate compound containing four or more (meth) acryloyl groups in a molecule, which is an arbor molecular compound containing an ether bond or an ester bond and having a (meth) acryloyl group disposed at its terminal, is a commercially available product. Examples of the compound include V # 1000 (compound of formula (11) having a molecular weight of 2800, manufactured by Osaka Chemical Industries, Ltd.). In addition, in this invention, molecular weight is a number average molecular weight computed in polystyrene conversion by gel permeation chromatography (GPC).

In the present invention, examples of the method for synthesizing a tree compound having a dendrimer structure include a divergence method for advancing the synthesis from the core, which is the center, to the outside, and a convergence method for advancing the synthesis from the outside, to the core. Synthetic methods are known to those skilled in the art and are described, for example, in Japanese Patent Laid-Open No. 11-60540. Specifically, the tree compound of the first generation can be produced by reacting a polyester polyol compound obtained by reacting dipentaerythritol with 2,2-dimethylolpropionic acid with (meth) acrylic acid. In addition, a second generation of a tree compound can be prepared by further reacting the polyester polyol compound with 2,2-dimethylolpropionic acid and then with (meth) acrylic acid.

In this invention, 0.01-25 weight% is preferable with respect to the weight of (A) component-(D) component, Preferably it is 0.5-10 weight%.

The photocurable prepolymer which is (B) component in this invention is a base resin (base oligomer) of an adhesive composition, and is a photosensitive resin by which the (meth) acryloyl group which is a reactor polymerizes by irradiation of active energy rays, such as an ultraviolet-ray. The component (B) is a transparent, low hygroscopic resin, and has a very low polarity and molecular structure, and thus is a component that blocks oil or water from entering the outer periphery of the bonding surface.

(B) The photocurable prepolymer of the present invention, which has one or more (meth) acryloyl groups, and is a hydrogenated additive of polybutadiene, polyisoprene, polybutadiene or polyisoprene, and a carboxy-modified modification of polybutadiene or polyisoprene. (Meth) acryloyl group-containing oligomers having at least one main chain skeleton selected from the group consisting of water and a polyester skeleton via a urethane bond and having at least one (meth) acryloyl group at the terminal or side chain of the main chain skeleton Can be mentioned. In the present invention, the photocurable prepolymer (B) preferably has a main chain skeleton selected from the group consisting of polybutadiene or hydrogenated additives of polybutadiene, and particularly preferably has a hydrogenated additive of polybutadiene as a main chain skeleton. Moreover, in this invention, it is preferable that (B) photocurable prepolymer has two or more (meth) acryloyl groups, and it is especially preferable to have a (meth) acryloyl group in the both ends of a main chain skeleton. In the present invention, the component (B) may be used alone, or two or more kinds thereof may be used in combination.

In this invention, the molecular weight of the photocurable prepolymer of (B) component is 400-200,000 normally, 800-100,000 are preferable and 1,000-30,000 are more preferable. If it is such a molecular weight, a viscosity will be in a suitable range, and applicability | paintability of a syringe will be favorable, and the cure shrinkage of the hardened | cured material of the active-energy-ray-curable composition after adhesion does not become large.

The photocurable prepolymer of (B) component is a commercial item "Nisso (NISSO) -PB TEAI-1000" by Nippon Soda Co., Ltd. (both terminal acrylate modified hydrogenated butadiene-type oligomer), "Nisso-PB TE by Nippon Soda company" -2000 "(both terminal methacrylate-modified butadiene oligomers)," UC-203 "by Kuraresa (the esterified oligomer of the maleic anhydride adduct of an isoprene polymer and 2-hydroxyethyl methacrylate), Kagawa Chemical "UA-1" (terminal urethane acrylate-modified polybutadiene hydrogenated substance) etc. are mentioned.

In this invention, 25-60 weight% is preferable with respect to the weight of (A) component-(D) component, and it is more preferable that it is 30-50 weight%.

In the present invention, the monofunctional or bifunctional (meth) acryloyl group-containing monomer ((meth) acrylate monomer) as the component (C) is a reactive diluent, and solidifies the base resin at the time of curing, thereby providing excellent adhesion to the adherend. It is also an ingredient to exert.

As (C) component, the (meth) acrylate which has a polar group, for example, the (meth) acrylate containing a hydroxyl group, the (meth) acrylate containing a carboxyl group, and the acrylate containing an amino group; (Meth) acrylate monomers which have a low polar molecular structure, for example, an aliphatic (meth) acrylate monomer, an alicyclic (meth) acrylate monomer, and an aromatic (meth) acrylate monomer are mentioned.

These (meth) acrylate monomers may be monofunctional (meth) acrylate monomers, may be bifunctional (meth) acrylate monomers, may be used independently, respectively, or may be used in combination of 2 or more type.

As a (meth) acrylate monomer containing a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2, for example -Hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, and glycerol mono (meth) acrylate are mentioned.

As a (meth) acrylate monomer containing a carboxyl group, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl Hexahydrophthalic acid is mentioned.

As a (meth) acrylate monomer containing an amino group, diethylaminoethyl (meth) acrylate and dimethylaminomethyl (meth) acrylate are mentioned, for example.

Aliphatic (meth) acrylates are, for example, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, 1,6-hexane Diol (meth) acrylate is mentioned.

As aromatic (meth) acrylate, benzyl (meth) acrylate is mentioned, for example.

Alicyclic (meth) acrylate is a (meth) acrylate which has a C3-C20 monocyclic or polycyclic alicyclic hydrocarbon group, For example, cyclohexyl (meth) acrylate and isobornyl (meth) acryl The rate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, tricyclo decanyl (meth) acrylate, norbornyl (meth) acrylate, etc. are mentioned.

These monofunctional or bifunctional (meth) acryloyl group-containing monomers are "SA-1002" (manufactured by Mitsubishi Chemical Corporation), "Kayarad R-684" (manufactured by Nippon Kayaku), "Lightester BZ", " Light ester IB-X "," light ester HO "," light ester HO-MS "(" light ester "are all manufactured by Kyoeisha Chemical Co., Ltd.), etc. are mentioned as a commercial item.

In this invention, 25-70 weight% is preferable with respect to the weight of (A) component-(D) component, and it is more preferable that it is 40-60 weight%.

(D) component in this invention is a photoinitiator. Although a photoinitiator can mention an ultraviolet-ray polymerization initiator, a visible light polymerization initiator, etc., All are used without a restriction | limiting. Examples of the ultraviolet polymerization initiator include benzoin, benzophenone, acetophenone, and the like, and examples of the visible light polymerization initiator include acylphosphine oxide, thioxanthone, metallocene and quinone.

Specific examples of the ultraviolet polymerization initiator include benzophenone-based polymerization initiators such as benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid and bisdiethylaminobenzophenone; Acetophenone type polymerization initiators, such as 2, 2- diethoxy acetophenone; Benzoin-based polymerization initiators such as benzyl, benzoin and benzoin isopropyl ether; Alkylphenone-based polymerization initiators such as benzyl dimethyl ketal; Thioxanthone type polymerization initiators, such as thioxanthone; 1-hydroxycyclohexylphenyl ketone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2 And hydroxyalkylphenone-based polymerization initiators such as -hydroxy-2-methyl-1-propan-1-one and 2-hydroxy-2-methyl-1-phenylpropan-1-one.

Visible light polymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4 Acylphosphine oxide photoinitiators such as, 4-trimethyl-pentylphosphine oxide; Campoquinone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Ketone system polymerization initiators, such as 1-butanone-1, etc. are mentioned.

In the present invention, as the photopolymerization initiator (D), preferably 1-hydroxycyclohexylphenyl ketone (IRGACURE 184, manufactured by Ciba Specialty Chemicals) and bis (2,4,6-trimethylbenzoyl)- Phenylphosphine oxide (Irgacure 819, manufactured by Ciba Specialty Chemicals, Inc.).

In this invention, 0.1-10 weight% is preferable and, as for (D) component, with respect to the weight of (A) component-(D) component, it is more preferable that it is 0.5-5 weight%.

The energy-beam curable resin composition of this invention is various elastomers, such as an inorganic filler, antioxidant, a polymerization inhibitor, a plasticizer, an organic filler, an acrylic rubber, a urethane rubber, and methyl methacrylate in the range which does not impair the objective of this invention. Graft copolymers such as butadiene-styrene graft copolymers and acrylonitrile-butadiene-styrene graft copolymers, solvents, extenders, reinforcing agents, thickeners, dyes, pigments, flame retardants and surfactants, and additives such as thermal polymerization initiators Can be used.

The curable composition of this invention can contain an inorganic filler further as (E) component for the purpose of further providing high hardness, resin rigidity, and low hardening shrinkage property.

Examples of the inorganic fillers include silica powders such as quartz, quartz glass, fused silica and spherical silica, oxides such as spherical alumina, crushed alumina, magnesium oxide, beryllium oxide and titanium oxide, and nitrides such as boron nitride, silicon nitride and aluminum nitride. Logistics, carbides such as silicon carbide, hydroxides such as aluminum hydroxide and magnesium hydroxide, metals such as copper, silver, iron, aluminum, nickel and titanium, alloys, carbon fillers such as diamond and carbon, and composite oxides And glass fillers to be mentioned. These inorganic fillers may be used alone or in combination of two or more. About an inorganic filler, it is easily available, As a commercial item, it is a glass filler ("CF0023-05C" by Nippon-Frit Co., Ltd.), amorphous silica ("Shistar KE-P250" by Nippon Shokubai Co., Ltd.), fumed silica (a thixotropy) Imparting agent) ("TG308F" by Cabot Specialty Chemicals Co., Ltd.), and spherical silica ("CF0018-WB15C" by Nippon Frit Co., Ltd.) is mentioned. In consideration of the filling property to the acrylic resin in the present invention, a dimming glass filler containing a composite oxide having a refractive index adjusted is preferable, and a spherical shape is preferable in order not to increase the viscosity at that time.

In this invention, 70-300 weight part is preferable with respect to a total of 100 weight part of (A) component-(D) component, and 100-250 weight part is more preferable.

The curable composition of this invention can contain antioxidant further as (F) component for the purpose of stability of a composition.

As antioxidant, a phenolic antioxidant, hydroquinone type antioxidant, and other antioxidant are mentioned, Preferably it is a phenolic antioxidant.

Phenolic antioxidants include 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol), catechol, picric acid, tertiary butylcatechol, 2,6-dibutylbutyl-p-cresol and 4 And 4'-thiobis [ethylene (oxy) (carbonyl) (ethylene)] bis [2,6-bis (1,1-dimethylethyl) phenol].

Hydroquinone antioxidants include β-naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, monobutyl butylhydroquinone, 2,5-dibutylbutyl hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone and 2,5-dibutylbutyl-p-benzoquinone are mentioned.

Examples of other antioxidants include citric acid, phenothiazine, 2-butyl-4-hydroxyanisole, and the like.

Antioxidants include Irganox 1010 and Irganox 1035FF (both manufactured by Ciba Specialty Chemicals) as commercially available products.

In this invention, 0.01-5 weight part is preferable with respect to a total of 100 weight part of (A) component-(D) component, and 0.1-2 weight part is more preferable.

The curable composition of this invention can contain a polymerization inhibitor further as (G) component.

As a polymerization inhibitor, a phenol type polymerization inhibitor and a phenothiazine type polymerization inhibitor are mentioned.

Phenolic polymerization inhibitors include 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol) (BHT), catechol, picric acid, tertiary butyl catechol, 2,6-dibutyl butyl-p- Cresol and 4,4'- thiobis [ethylene (oxy) (carbonyl) (ethylene)] bis [2, 6-bis (1, 1- dimethylethyl) phenol] are mentioned.

Phenothiazine-based polymerization inhibitors include phenothiazine, bis (α-methylbenzyl) phenothiazine, 3,7-dioctylphenothiazine and bis (α, α-dimethylbenzyl) phenothiazine.

Moreover, phenolic polymerization inhibitors, such as BHT, can also be used as antioxidant.

In this invention, 0.01-3 weight part is preferable with respect to a total of 100 weight part of (A) component-(D) component, and 0.05-1 weight part is more preferable.

The curable composition of this invention can contain a (H) plasticizer for the purpose of not only improving adhesiveness and adhesive durability further, but also improving the heat resistance of a hardening body. As such a plasticizer, the oligomer obtained by epoxidizing the unsaturated bond of polybutadiene is preferable, As a commercial item, BF-1000 (made by Adeka) or PB-3600 (made by Daicel Kogyo Co., Ltd.) etc. are mentioned. have.

In the curable composition of the present invention, the component (H) is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total of the components (A) to (D).

The active energy ray curable resin composition of this invention can contain (I) organic filler for the purpose of further lowering a cure shrinkage rate. Examples of the organic fillers include acrylic fillers, styrene fillers, acrylic / styrene copolymer fillers, fluorine resin fillers, polyethylene fillers, and polypropylene fillers. Commercially available products include "PPW-5" (polypropylene fillers, Seishin Corp.). Manufacture) and "Profile Mat 31" (polypropylene filler, manufactured by MICROOPDERDERS, INC.). Each may be used independently, or may be used in combination of 2 or more type. Preferred organic fillers are polypropylene fillers with low swelling.

In the curable composition of the present invention, the component (I) is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total of the components (A) to (D).

The curable composition of this invention can contain a silane coupling agent further for the purpose of further improving adhesiveness with respect to a glass surface.

As the silane coupling agent, γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyl Trimethoxysilane, γ-acryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimeth Oxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane and γ- Ureidopropyltriethoxysilane, etc., Preferably, (gamma)-glycidoxy propyl trimethoxysilane, (gamma)-glycidoxy propyl triethoxysilane, 2- (3, 4- epoxycyclohexyl) ethyl is mentioned. Trimethoxysilane and γ-glycidoxypropylmethyldiethoxysilane. These silane coupling agents can also be used individually or in combination of 2 or more types.

In the curable composition of the present invention, the content of the silane coupling agent is preferably 0 to 10 parts by weight based on 100 parts by weight of the total of the components (A) to (D). However, since a silane coupling agent tends to come out as an outgas component at the time of the heat test after hardening of a curable composition, it is in the total weight of the curable composition which does not contain a silane coupling agent, ie, (A) component-(D) component. It is preferable that content of a silane coupling agent is 0 weight part with respect to.

In the present invention, the cured product of the active energy ray curable resin composition is obtained by curing the active energy ray curable resin composition of the present invention. The method of hardening the active energy ray curable resin composition of this invention includes the process of irradiating an active energy ray to the active energy ray curable resin composition of this invention.

In this invention, if the wavelength of an active energy ray curable resin composition of this invention hardens, it will not specifically limit, It is 100-420 nm, More preferably, it is 300-420 nm.

The active energy ray curable resin composition of this invention is an adhesive composition, and is useful as an adhesive agent, especially the adhesive agent for bonding optical components.

As the member to be bonded using the adhesive of the present invention, a small part containing a metal, a metal plated member, a plastic, or the like can be mentioned. Examples of the metal constituting the small part include Mg, Zn, Ni, and Al. Examples of the plastic include liquid crystal polymers (LCP), cycloolefin polymers (COP), cycloolefin copolymers (COC), and polyphenylene sulfide ( PPS), polyphenylene oxide (PPO), the composite plastic material which knead | mixed glass fiber and carbon fiber to the said plastic material, etc. are mentioned. The plastic material is available as a commercial item, and PPS includes "Idemitsu PPS" manufactured by Idemitsu Co., Ltd. and "Torerina" manufactured by Toray Industries. The liquid crystal polymer is manufactured by Toray Corporation "Siberas", manufactured by Polyplastics. "Vectra" can be mentioned, As a polyarylate, "U polymer" by a unityca company is mentioned, As a cycloolefin polymer, "Zonex" by Nihon Zeon company, "Apel" by Mitsui Chemical Industries, Ltd., and JSR company are mentioned. The "Aton" can be mentioned, As a polycarbonate, Although the "Panlite" by Deijin Co., etc. are mentioned, It is not limited to these.

In addition, as an optical component bonded to each other using the adhesive of the present invention, a member of an apparatus used in the field of equipment used for recording and reproducing recording materials, for example, a light detector (PD), a laser diode (LD), a lens, The optical module in which optical components, such as a prism, and optical components, such as a lens, are mounted is mentioned. In addition, optical pick-up components have different requirements for fixed accuracy depending on the components. Specifically, components having high precision requirements such as photodetector PD, laser diode LD, condenser lens NAL, and half mirror ( Parts with high demands such as beam splitter (HM (PBS)), skew, etc., parts with medium demand for high precision such as reflection mirror (RM), objective lens (OBL), collimator lens, etc. A part with a slightly lower precision requirement can be mentioned.

The curable composition of the present invention contains a photofunctional curable prepolymer which is a polyfunctional acrylate compound, a diene-based or hydrogenated diene-based (meth) acrylate, a reaction dilutable (meth) acrylate having various functional groups, and a photopolymerization initiator. Since it has a specific composition, it can be cured in a short time by irradiating an active energy ray, and has high initial adhesiveness with respect to a plastic member or metal member, such as polyphenylene sulfide (PPS), and durability test including high temperature, high humidity test. It is characterized by high retention at. Its deformation at hot time and deformation at hot time and load are very little suppressed. For this reason, the movement of the component after hardening adhere | attached by the active-energy-ray-curable resin composition of this invention can be suppressed to the maximum.

[Example]

Although an Example and a comparative example are given to the following and this invention is demonstrated in detail, this invention is not limited to this. In addition, the following compounds were selected for each component in the compounding composition described in the Example and the comparative example.

(A) polyfunctional acrylate compound

(A-1) V # 802 (manufactured by Osaka Yuki Chemical Co., Ltd.)

(A-2) dipentaerythritol hexaacrylate ("DPE-6A" manufactured by Kyoeisha Chemical Co., Ltd.)

(A-3) V # 1000 (manufactured by Osaka Yuki Chemical Co., Ltd.)

(A-4) V # star-501 (manufactured by Osaka Yuki Chemical Co., Ltd.)

(B) photocurable prepolymer

(B-1) Terminal urethane acrylate-modified polybutadiene ("TE-2000" by Nippon Soda Co., Ltd.)

(B-2) Terminal urethane acrylate-modified polybutadiene hydrogenated substance ("UA-24" by Kagawa Chemical Corporation)

(C) Monofunctional or bifunctional (meth) acryloyl group containing monomer (acrylate monomer)

(C-1) Tricyclodecane dimethanol acrylate ("SA-1002" by Mitsubishi Chemical Corporation)

(C-2) benzyl methacrylate ("light ester BZ" manufactured by Kyoeisha Chemical Co., Ltd.)

(C-3) Isobornyl methacrylate ("Light ester IB-X" manufactured by Kyoeisha Chemical Co., Ltd.)

(C-4) 2-hydroxyethyl methacrylate ("light ester HO" manufactured by Kyoeisha Chemical Co., Ltd.),

(C-5) 2-methacryloyloxyethyl succinic acid ("light ester HO-MS" by Kyoeisha Chemical Co., Ltd.)

(D) a photopolymerization initiator

(D-1) 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184" by Ciba Specialty Chemicals)

(D-2) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ("Irgacure 819" by Ciba Specialty Chemicals)

(E) inorganic filler

(E-1) Glass Filler ("CF0023-05C" manufactured by Nippon Frit Co.)

(E-2) Fumed Silica ("TG308F" by Cabot Specialty Chemicals)

(F) antioxidant

(F-1) ("Irganox 1010" manufactured by Ciba Specialty Chemicals)

(F-2) (Irganox 1035, manufactured by Ciba Specialty Chemicals)

(G) polymerization inhibitor

(G-1) 2,2-methylene-bis (4-methyl-6-tert-butylbutylphenol) ("BHT" by Kanto Chemical Co., Ltd.)

(H) plasticizer

(H-1) Oligomer obtained by epoxidizing unsaturated bond of polybutadiene ("BF-1000" manufactured by Adeka Co., Ltd.)

(I) component: organic filler

(I-1) Polypropylene filler ("PPW-5" by Seishin Corp.)

Various physical properties of the cured product of the active energy ray curable composition were measured as follows.

[Photocuring conditions]

As an active energy source, a spot irradiator ("LC-8" manufactured by Hamamatsu Hotonix Co., Ltd.) was used, and an ultraviolet intensity meter "UIT-101" manufactured by Ushio Corporation was used under conditions of an irradiation intensity of 250 mW / cm 2. Irradiated for a second to cure.

[Angle change measurement]

(1) Preparation of sample for measuring angle change

As shown in FIG. 1, the aluminum plate 2 is fixed vertically, and a 300 micrometers gap is made and the SUS board 4 (SUS304, 10 (fixed side) x 1.0 (thickness) x 20 (length) mm) is made. 1.5 g) was placed on the pedestal 5 so as to be approximately 90 degrees with respect to the aluminum plate. The active energy ray curable resin composition (1) (0.0025 cc) of this invention was apply | coated using the dispenser regulator (Musashi Engineering-made ML-606) in the center part of the fixed edge so that an aluminum plate and an SUS board may be fixed. Immediately after application, the UV light of 250 mW / cm 2 was irradiated and fixed for 12 seconds using a UV irradiator 3 at a distance of 45 degrees and 20 mm at an angle. Next, the pedestal 5 was removed to obtain a sample for evaluation.

(2) measuring the change of angle

The deformation | transformation of the adhesive part at the time of heat was monitored from an angle change using the tilt sensor (MTS-T20 by NISSHO ELECTRONICS). As shown in Fig. 2, the sample for measuring the angle change described above is fixed in a thermostat (MC-711T, manufactured by ESPEC), and tilted so that the beam of the tilt sensor is reflected on the SUS plate for monitoring. The position of the sensor was adjusted. The temperature in the thermostat was heated by holding at 25 ° C. for 30 minutes. The amount of change in angle after temperature regulation was measured and made into zero. The temperature cycle is kept at 25 ° C. for 1 hour, and then the temperature is raised from 25 ° C. to 60 ° C. for 30 minutes, after reaching 60 ° C. for 1 hour at 60 ° C., and further for 30 minutes from 60 ° C. to 80 ° C. Was raised, and after reaching | attaining 80 degreeC, it hold | maintained at 80 degreeC for 1 hour, and it was made into 1 cycle by decreasing temperature from 80 degreeC to 25 degreeC for 30 minutes. In this temperature cycle, the temperature in the thermostat was changed to 25 ° C, 60 ° C and 80 ° C. In the first cycle, the angle change amount after holding for 1 hour at 60 ° C and 80 ° C and holding for 1 hour at 25 ° C after one cycle was determined. In addition, the angle change amount in a table | variety changes with minutes.

[Adhesive test]

The adhesion test was measured by puncture adhesion strength. As shown in Fig. 3, aluminum chips (engineering test service company, A5052P, 10 mm × 10 mm × 10 mm × 2 mm in height) polished end faces on PPS (polyphenylene sulfide, Idemitsu PPS NT7790 (manufactured by Idemitsu Corporation)) ), And apply 0.0025 cc of active energy ray-curable resin composition using a syringe using a dispenser regulator (ML-606 manufactured by Musashi Engineering, Inc.), and then use a UV irradiator (LC6, manufactured by Hamamatsu Corporation) at a distance of 20 mm. UV light of 250 mW / cm 2 was fixed for 12 seconds using a UV illuminometer (UIT-101, manufactured by Ushio Denki Co., Ltd.). Thus, the adhesive test piece was produced. Using a punching tester (AGS-500D manufactured by Shimadzu Corporation), the punching strength was measured at a punching speed of 10 mm / min from the side where the chip was not fixed at a diameter of 4 mm. The thing which showed the state without lifting peeling at the strength of 40 N or more was made into (circle). The same test was carried out with a PPS chip (10 mm in length × 10 mm in width × 2 mm in height), a PPS plate, and an aluminum chip and an aluminum plate (A5052P manufactured by Engineering Test Service Co., Ltd.) polished at the end face.

(Examples 1 to 7 and Comparative Examples 1 to 2)

The raw material of the kind shown in following Table 1 and Table 2 was mixed by the composition shown in Table 1 and Table 2, and the resin composition was manufactured. About the obtained composition, the measurement of adhesive strength and moisture resistance, heat resistance, and the heat shock evaluation test were done. These results are shown in Table 1 and Table 2. In addition, content is a weight part.

The moisture resistance test was performed under conditions of 65 ° C / 95% RH-336 hours using LH21-21M (manufactured by Nagano Science Co., Ltd.). Lifting peeling or cracking and cracking at the end were not observed, and the adhesive strength was 40 N or more.

Heat resistance was performed on the conditions of 80 degreeC-336 hours using LC-112 (made by EPSP Co., Ltd.). Lifting peeling or cracking and cracking at the end were not observed, and the adhesive strength was 40 N or more.

The heat shock evaluation test was performed on 100 cycle conditions of -40 degreeC (30 minutes) / 85 degreeC (30 minutes) using TSA-41L (made by EPSP Co., Ltd.). Lifting peeling or cracking and cracking at the end were not observed, and the adhesive strength was 40 N or more.

Since the curable composition of this invention can fix optical components, such as LD, a photodetector, a lens, and a prism, optical modules, etc. with which optical components, such as a lens, are mounted with high fixed precision, optical device assembly It is useful as an adhesive for use.

1 active energy ray curable resin composition
2 aluminum plate
3 UV irradiator
4 SUS plate
5 pedestal
6 tilt sensors
7 active energy ray curable resin composition
8 aluminum plate
9 PPS version

Claims (7)

As active energy ray curable resin composition, following (A) component-(D) component:
(A) (a1) a linear or branched multimer thereof having a glycerol derivative and an ether skeleton as a linking functional group,
(a2) a linear or branched multimer thereof having a trimethylolpropane derivative and an ether skeleton as a linking functional group,
(a3) linear or branched multimers thereof having a monomer and an ether skeleton of a pentaerythritol derivative as a linking functional group and
(a4) A tree-like molecular compound comprising an ether bond or an ester bond and having a (meth) acryloyl group disposed at four or more ends thereof.
A polyfunctional acrylate compound containing four or more (meth) acryloyl groups in a molecule, selected from the group consisting of
(B) photocurable prepolymer,
(C) a monofunctional or bifunctional (meth) acryloyl group-containing monomer and
(D) a photopolymerization initiator
It contains an active energy ray curable resin composition. The active energy ray curable resin composition according to claim 1, wherein the component (A) is 0.01 to 25% by weight based on the weight of the components (A) to (D). The active energy ray curable resin composition according to claim 1 or 2, which is an adhesive for bonding optical components. The active energy ray curable resin composition according to claim 1 or 2, which is an adhesive for assembling an optical pickup device. The adhesive structure bonded together by the active-energy-ray-curable resin composition of Claim 1 or 2. The optical component bonded together using the active energy ray curable resin composition of Claim 3. An optical pickup apparatus assembled using the active energy ray curable resin composition according to claim 4.

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