JP2009173863A - Adhesive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photo-curable or electron beam-curable adhesive resin composition which has excellent adhesion to adherends such as metal oxides and metals, and is high in glass transition temperature after curing and suitable as an adhesive material for electronic components. <P>SOLUTION: A photo-curable or electron beam-curable adhesive resin composition containing a bifunctional urethane (meth)acrylate oligomer (A) and a monomer component (B) is provided, wherein the urethane (meth)acrylate oligomer (A) contains a urethane prepolymer moiety composed of a polycarbonate diol and a polyisocyanate and the repetition number (n) of the urethane prepolymer moiety is 10-30, and the monomer component (B) contains a cyclic monomer having a (meth)acryloyl group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is an adhesive resin composition, in particular, a photo-curing which is excellent in adhesion to an adherend such as a metal oxide or a metal and has a high glass transition temperature after curing and is suitable as an adhesive material for electronic parts. Or an electron beam curable adhesive resin composition.

  Conventionally, thermosetting adhesives are known as adhesives for bonding electronic parts, machine parts, and the like. However, since the thermosetting adhesive has a long curing time, there is a problem in that productivity is lowered when components are bonded using the thermosetting adhesive. On the other hand, a light or electron beam curable adhesive has been developed for bonding the above components, and the light or electron beam curable adhesive can be bonded in a very short time by irradiation with light or electron beam. Because it is completed, productivity can be improved.

  For example, JP-A No. 2004-115757 (Patent Document 1) discloses an ethylenic compound in which a urethane (meth) acrylate having a number average molecular weight of 10,000 to 40,000 is 30 to 70% by weight and a glass transition temperature of a homopolymer is 60 ° C. or higher. A liquid curable resin composition containing 30 to 60% by weight of an unsaturated monomer is disclosed. The liquid curable resin composition has excellent adhesion to a plastic substrate, and is excellent in heat resistance and water resistance, and is useful for adhesion of various parts such as a laminate of a vinyl chloride sheet and a PET film. It is disclosed.

JP 2004-115757 A

  By the way, in the recent assembly of electronic components, it is necessary to simultaneously bond a metal such as gold or nickel and a metal oxide such as IZO or ITO as an adherend. First, an adhesive having excellent adhesion to various adherends is required. On the other hand, when the present inventor examined, an adhesive resin composition containing a urethane (meth) acrylate oligomer synthesized using a polyether polyol composed of a propylene oxide (PO) chain is a metal such as gold, IZO. It was found to have sufficient adhesive strength (peel strength) to metal oxides such as.

  On the other hand, an adhesive material used for assembling an electronic component is required to have a sufficiently high glass transition temperature because of its use conditions. In view of this point, the present inventors have examined that an adhesive resin composition containing a urethane (meth) acrylate oligomer synthesized using a polyether polyol composed of the PO chain is an adhesive resin after light or electron beam curing. It has been found that there is room for improvement in use as an adhesive material for electronic parts because of its low glass transition temperature.

  Accordingly, the object of the present invention is to solve the above-mentioned problems of the prior art, and has excellent adhesion to adherends such as metal oxides and metals, and has a high glass transition temperature after curing, which is suitable as an adhesive material for electronic components. Another object is to provide a photocurable or electron beam curable adhesive resin composition.

  As a result of intensive studies to achieve the above object, the inventors of the present invention include a urethane prepolymer portion composed of polycarbonate diol and polyisocyanate, and the number of repetitions (n) of the urethane prepolymer portion is in a specific range. A photocurable or electron beam curable adhesive resin composition containing a bifunctional urethane (meth) acrylate oligomer (A) and a cyclic monomer having a (meth) acryloyl group is a metal oxide such as IZO, In addition to excellent adhesion to metals such as gold, it was found that the glass transition temperature after curing was high, and the present invention was completed.

That is, the adhesive resin composition of the present invention is a photocurable or electron beam curable adhesive resin composition containing a bifunctional urethane (meth) acrylate oligomer (A) and a monomer component (B). ,
The urethane (meth) acrylate oligomer (A) includes a urethane prepolymer part composed of polycarbonate diol and polyisocyanate, and the number of repetitions (n) of the urethane prepolymer part is 10 to 30,
The monomer component (B) includes a cyclic monomer having a (meth) acryloyl group.

  In a preferred example of the adhesive resin composition of the present invention, the number average molecular weight of the polycarbonate diol used for forming the urethane prepolymer part of the urethane (meth) acrylate oligomer (A) is 500 to 4000.

  In another preferable example of the adhesive resin composition of the present invention, the cyclic monomer having a (meth) acryloyl group is acryloylmorpholine.

  In the adhesive resin composition of this invention, the ratio of the said urethane (meth) acrylate oligomer (A) in the total compounding quantity of the said urethane (meth) acrylate oligomer (A) and the said monomer component (B) is 10-. It is preferable that the proportion of the cyclic monomer having 80% by mass and having the (meth) acryloyl group is 20 to 90% by mass.

  In the adhesive resin composition of the present invention, the polyisocyanate is preferably hydrogenated diphenylmethane diisocyanate and isophorone diisocyanate.

  The adhesive resin composition of the present invention preferably further contains a photopolymerization initiator (C).

  The adhesive resin of the present invention is obtained by curing the above adhesive resin composition by light or electron beam irradiation, has a glass transition temperature (Tg) of 80 ° C. or higher, and a peel strength of 300 N for gold and IZO. It is characterized by being / m or more.

  According to the present invention, a bifunctional urethane (meth) acrylate oligomer (A) comprising a urethane prepolymer portion comprising a polycarbonate diol and a polyisocyanate, wherein the urethane prepolymer portion has a repeating number (n) in a specific range. And a cyclic monomer having a (meth) acryloyl group, which has excellent adhesion to metal oxides such as IZO and metals such as gold, and has a high glass transition temperature after curing, and is suitable as an adhesive material for electronic components. In addition, a photocurable or electron beam curable adhesive resin composition can be provided.

  The present invention is described in detail below. The adhesive resin composition of the present invention is a photocurable or electron beam curable adhesive resin composition comprising a bifunctional urethane (meth) acrylate oligomer (A) and a monomer component (B), The urethane (meth) acrylate oligomer (A) includes a urethane prepolymer portion composed of a polycarbonate diol and a polyisocyanate, and the repeating number (n) of the urethane prepolymer portion is 10 to 30, and the monomer component (B ) Comprises a cyclic monomer having a (meth) acryloyl group. Since the adhesive resin composition of the present invention is cured by irradiation with light or an electron beam, the adhesion can be completed in an extremely short time, and excellent adhesion to a metal oxide such as IZO and a metal such as gold. Furthermore, the glass transition temperature after curing is high, and it is suitable as an adhesive material for electronic parts.

［式中、Ｒ¹及びＲ²は、上記と同義であり、ｎはウレタンプレポリマー部の繰り返し数である］で表わされるウレタンプレポリマーを合成し、該ウレタンプレポリマーに下記一般式(IV)：
ＣＨ₂＝Ｃ(Ｒ⁴)−ＣＯＯ−Ｒ³−ＯＨ ・・・ (IV)
［式中、Ｒ³は２価の基であり、Ｒ⁴は水素又はメチル基である］で表わされる水酸基を有する(メタ)アクリレートを付加させることによって製造することができ、具体的には、下記一般式(V)：

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴及びｎは、上記と同義である］で表わすことができる。 The urethane (meth) acrylate oligomer (A) used in the adhesive resin composition of the present invention is bifunctional and has a (meth) acryloyloxy group (CH ₂ ═CHCOO— or CH ₂ ═C (CH ₃ ) COO—). 2 and having a plurality of urethane bonds (—NHCOO—), for example, the following general formula (I):
HO-R ¹ -OH (I)
[Wherein R ¹ is a divalent group having a carbonate bond] and the following general formula (II):
^{OCN-R 2 -NCO ··· (II} )
From the polyisocyanate represented by the formula [wherein R ² is a divalent group], the following general formula (III):

[Wherein R ¹ and R ² are as defined above, and n is the number of repetitions of the urethane prepolymer part], and the urethane prepolymer is synthesized with the following general formula (IV): :
^{_{CH 2 = C (R 4)}} -COO-R 3 -OH ··· (IV)
[Wherein R ³ is a divalent group and R ⁴ is hydrogen or a methyl group] can be produced by adding a (meth) acrylate having a hydroxyl group represented by The following general formula (V):

[Wherein R ¹ , R ² , R ³ , R ⁴ and n are as defined above].

  Here, the urethane (meth) acrylate oligomer (A) used in the adhesive resin composition of the present invention has a repeating number (n) of the urethane prepolymer portion composed of polycarbonate diol and polyisocyanate of 10 to 30, preferably Is 10-25. When the number of repeating urethane prepolymer parts (n) is less than 10, the adhesion to various adherends is low. On the other hand, when it exceeds 30, the synthesis of the oligomer is difficult.

In addition, the repeating number (n) of the urethane prepolymer part is an average repeating number. Specifically, the number average molecular weight (Ma) of the urethane (meth) acrylate oligomer (A), the number average molecular weight of the polycarbonate diol ( Mb), the molecular weight of the polyisocyanate (Mc), and the molecular weight (Md) of the (meth) acrylate having a hydroxyl group, the following formula:
n = (Ma−2 × Md−Mc) / (Mb + Mc)
Can be asked according to. In the present invention, the number average molecular weight (Ma) of the urethane (meth) acrylate oligomer (A) is a value determined in terms of polystyrene using GPC, and the number average molecular weight (Mb) of the polycarbonate diol is GPC. Is a value obtained from a calibration curve prepared with monodisperse polypropylene glycol (PPG).

The polycarbonate diol used for the synthesis of the urethane prepolymer is a compound having a plurality of carbonate bonds (—OCOO—) and two hydroxyl groups. R ¹ in the formula (I) is a divalent group having a carbonate bond. For example, the formula: — (ROCOO) _m ROCO— [wherein R is an ethylene group, a propylene group, a tetramethylene group, etc. An alkylene group, and m is the number of repeating alkylene carbonate units].

  Examples of the polycarbonate diol include those obtained by a dehydrochlorination reaction between a dihydric alcohol and phosgene and a transesterification reaction between a dihydric alcohol and a carbonate ester. Here, as the dihydric alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, Examples include 3-methyl-1,5-pentanediol and 1,6-hexanediol. Examples of the carbonate ester include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, alkylene carbonates such as ethylene carbonate and propylene carbonate, and diaryl carbonates such as diphenyl carbonate. These polycarbonate diols may be used alone or in combination of two or more.

  The polycarbonate diol used for the synthesis of the urethane prepolymer preferably has a number average molecular weight of 500 to 4000, and more preferably 1000 to 3000. If the number average molecular weight of the polycarbonate diol to be used is less than 500, gelation tends to occur when the prepolymer is synthesized, and stable synthesis is difficult. On the other hand, if it exceeds 4000, the adhesiveness is lowered, which is not preferable.

The polyisocyanate used for the synthesis of the urethane prepolymer is a compound having two isocyanate groups. R ² in the formula (II) is a divalent group such as an alkylene group, a cycloalkylene group, an alkylene cycloalkylene group, a cycloalkylene alkylene cycloalkylene group, an arylene group, an alkylene arylene group, an arylene alkylene arylene group, etc. Examples of the alkylene group include a hexamethylene group, examples of the cycloalkylene group include a cyclohexylene group and a methylcyclohexylene group, and examples of the alkylene cycloalkylene group include 3-methylene-3. , 5,5-trimethylcyclohexylene group, etc., cycloalkylenealkylenecycloalkylene group, cyclohexylenemethylenecyclohexylene group, etc., arylene group, tolylene group, etc., alkylenearylene group, methylenephenylene group, etc. But ants The Ren alkylene arylene group, phenylene methylene phenylene group, and the like.

  Specific examples of the polyisocyanate include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), crude diphenylmethane diisocyanate (crude MDI), isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), and hydrogenated triisocyanate. Examples include diisocyanate and hexamethylene diisocyanate (HDI). Among these, hydrogenated diphenylmethane diisocyanate and isophorone diisocyanate are preferable. These polyisocyanates may be used alone or in combination of two or more.

  In the synthesis of the urethane prepolymer, it is preferable to use a catalyst for urethanization reaction. Examples of the catalyst for urethanization reaction include organic tin compounds, inorganic tin compounds, organic lead compounds, monoamines, diamines, triamines, cyclic amines, alcohol amines, ether amines, organic sulfonic acids, inorganic acids, titanium A compound, a bismuth compound, a quaternary ammonium salt, etc. are mentioned, Among these, an organotin compound is preferable. Suitable organic tin compounds include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiocarboxylate, tin octenoate, monobutyltin oxide, and the like.

The (meth) acrylate having a hydroxyl group to be added to the urethane prepolymer is a compound having one hydroxyl group and one (meth) acryloyloxy group. R ³ in the formula (IV) is a divalent group such as a divalent hydrocarbon group such as an alkylene group. Examples of the alkylene group include an ethylene group and a propylene group. R ⁴ in formula (IV) is hydrogen or a methyl group, and is preferably hydrogen.

  Specific examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. These (meth) acrylates having a hydroxyl group may be used alone or in combination of two or more.

In addition, the adhesive resin composition of the present invention includes a monomer component (B), and a part or all of the monomer component (B) is a cyclic monomer having a (meth) acryloyl group. The cyclic monomer having the (meth) acryloyl group has one or more rings and a compound having one or more (meth) acryloyl groups [CH ₂ ═CHCO— or CH ₂ ═C (CH ₃ ) CO—]. It is. Here, examples of the ring include morpholine ring, triazine ring, isobornyl, benzene ring and the like, and among these, a heterocyclic ring such as morpholine ring is preferable. Specific examples of the cyclic monomer having a (meth) acryloyl group include (meth) acryloylmorpholine, and acryloylmorpholine is preferred. The cyclic monomer having the (meth) acryloyl group may be used alone or in combination of two or more.

  The adhesive resin composition of the present invention may contain a monomer other than the cyclic monomer having the (meth) acryloyl group as the monomer component (B). Examples of the monomer include ethyl (meth) acrylate, isobutyl ( Examples include (meth) acrylate monomers such as (meth) acrylate, n-butyl (meth) acrylate, isoamyl (meth) acrylate, and butoxyethyl (meth) acrylate.

  In the adhesive resin composition of the present invention, the ratio of the urethane (meth) acrylate oligomer (A) in the total amount of the urethane (meth) acrylate oligomer (A) and the monomer component (B) is preferably It is 10-80 mass%, More preferably, it is 15-75 mass%. When the proportion of the urethane (meth) acrylate oligomer (A) is less than 10% by mass, sufficient adhesion is difficult to obtain, whereas when it exceeds 80% by mass, the viscosity is high and the coating property is lowered.

  Moreover, the ratio of the cyclic monomer having the (meth) acryloyl group in the total blending amount of the urethane (meth) acrylate oligomer (A) and the monomer component (B) is preferably 20 to 90% by mass. More preferably, it is 25-85 mass%. When the ratio of the cyclic monomer having a (meth) acryloyl group is less than 20% by mass, the viscosity is high and the coating property is lowered. On the other hand, when it exceeds 90% by mass, sufficient adhesion cannot be obtained.

  The adhesive resin composition of the present invention preferably further contains a photopolymerization initiator (C). In this case, the adhesive resin composition can be easily cured by irradiation with light such as ultraviolet rays. This photoinitiator (C) has the effect | action which starts superposition | polymerization of the urethane (meth) acrylate oligomer (A) mentioned above and a monomer component (B) by irradiating light.

  Examples of the photopolymerization initiator (C) include 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, 2,2-dimethoxy-2-phenylacetophenone, acetophenone diethyl ketal, alkoxyacetophenone, benzyldimethyl ketal, benzophenone and 3,3-dimethyl-4-methoxybenzophenone, benzophenone derivatives such as 4,4-dimethoxybenzophenone, 4,4-diaminobenzophenone, alkyl benzoylbenzoate, bis (4-dialkylaminophenyl) ketone, benzyl, benzylmethyl ketal, etc. Benzyl derivatives of benzoin, benzoin derivatives such as benzoin and benzoin isobutyl ether, benzoin isopropyl ether, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, Thiolene, thioxanthone and thioxanthone derivatives, fluorene, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6- Trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1,2-benzyl-2-dimethylamino-1- (morpholinophenyl) -butanone-1, etc. Is mentioned. One of these photopolymerization initiators (C) may be used alone, or two or more thereof may be used in combination.

  The blending amount of the photopolymerization initiator (C) is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the urethane (meth) acrylate oligomer (A) and the monomer component (B). When the blending amount of the photopolymerization initiator is less than 0.1 parts by mass, the effect of initiating photocuring of the adhesive resin composition is small. On the other hand, when it exceeds 10 parts by mass, the effect of initiating photocuring is saturated. The raw material cost of the conductive resin composition increases.

  The adhesive resin of the present invention is obtained by curing the above-mentioned adhesive resin composition by light or electron beam irradiation, and has a glass transition temperature (Tg) of 80 ° C. or higher, gold and IZO (indium). -Peel strength against zinc oxide) is 300 N / m or more. Here, the irradiation conditions of light or an electron beam are not specifically limited, It can set suitably. The adhesive resin of the present invention is excellent in adhesion to metal oxides such as IZO and metals such as gold, and has a high glass transition temperature, so that it is a low-temperature curable adhesive material for various electronic members such as components of electronic displays. Useful as. If the glass transition temperature (Tg) is less than 80 ° C., considering the usage environment of the electronic material, the cured resin may be softened, and if the peel strength against gold and IZO is less than 300 N / m, Insufficient adhesion to the body.

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

Example 1
Bifunctional polycarbonate diol having a number average molecular weight of 2600 [Nipporan 980R manufactured by Nippon Polyurethane Industry Co., Ltd.], 13.1 parts by mass of isophorone diisocyanate (IPDI), 0.01 parts by mass of dibutyltin dilaurate (DBTDL), and acryloylmorpholine (“Nikester A-MO” manufactured by Shin-Nakamura Chemical Co., Ltd.) 215.0 parts by weight was weighed into a 1-liter three-necked flask and allowed to react at 80 ° C. for 4 hours with stirring and mixing. A urethane prepolymer having an isocyanate group at the end was synthesized.

  Next, 0.3 parts by mass of 2-hydroxyethyl acrylate (2-HEA) is added to 100 parts by mass of the urethane prepolymer, and the mixture is reacted at 80 ° C. for 4 hours with stirring and mixing. 1) was synthesized. It was 40200 when the number average molecular weight of the obtained urethane acrylate oligomer (A-1) was measured by GPC.

  Next, 100.0 parts by mass of the urethane acrylate oligomer (A-1) (containing 65% by mass of acryloylmorpholine) and 1.0 part by mass of a photopolymerization initiator “Irgacure 184D” manufactured by Ciba Specialty Chemicals Co., Ltd. After stirring and mixing, vacuum-defoaming was performed to prepare a UV curable adhesive resin composition.

Next, samples for measuring peel strength for the following two types of adherends were prepared using the adhesive resin composition.
(1) Gold-treated film (2) IZO-treated PET film

<Preparation of peel strength measurement sample>
An adherend of about 18 × 15 cm is placed on a glass plate of about 40 × 40 cm, and an aluminum foil having a thickness of 50 μm with a central portion hollowed to a size of 10 × 8 cm is placed thereon as a spacer. A release PET film is partially sandwiched so that the gripping area of the chuck of the peel tester does not adhere. A small amount of UV curable adhesive resin composition is dropped on this, and then an easy-adhesion-treated PET film of about 18 × 15 cm is placed thereon. The UV curable adhesive resin composition is extended over the entire film surface with a roller from above the laminated film. This laminated film is placed on a base of about 15 × 15 × 1.5 cm with the easy-adhesion-treated PET film on top, and further, about 15 × 15 × 0.5 cm of quartz glass is placed on the film. This is UV cured by a conveyor type UV irradiator. In the conveyor type UV irradiator, the conveyor speed and the sample position (distance) were adjusted so that the integrated light amount was 3000 mJ. The cured film was cut with a width of 25 mm so that the margin was at the end, and a peel strength measurement sample was prepared.

  When the peel strength of the thus prepared sample was measured at a speed of 50 mm / min according to JIS K6854, (1) when the adherend was a gold-treated film, the peel strength was 376 N (2) When the adherend is an IZO-treated PET film, the peel strength is 761 N / m, and it can be seen that the adherend has a high peel strength. It was.

  In addition, using the adhesive resin composition, a sample of about 80 x 80 x 1 mm was made with a conveyor-type UV irradiator (integrated light intensity 3000 mJ), and about 60 x 10 x 1 mm from this plate sample A glass transition temperature measurement sample was cut out, and a dynamic viscoelasticity test was performed on the sample under conditions of a heating rate of 3 ° C / min and a frequency of 1 Hz, and the glass transition temperature of the cured resin was measured from the peak of tan δ As a result, it was found to be 170 ° C. and to have a glass transition temperature sufficient as an adhesive material for electronic components.

In addition, the repeating number (n) of the urethane prepolymer part of the urethane acrylate oligomer (A-1) used in the UV curable adhesive resin composition is the number average molecular weight 40200 of the urethane acrylate oligomer and the number average molecular weight of the polycarbonate diol. Calculation using 2600, molecular weight of polyisocyanate (IPDI) 222.28, molecular weight of acrylate chain (2-HEA) 116.11,
(40200−2 × 116.11−222.28) / (2600 + 222.28) = 14.1
Met.

(Example 2)
100.0 parts by mass of a bifunctional polycarbonate diol having a number average molecular weight of 1180 [N-981 manufactured by Nippon Polyurethane Industry Co., Ltd.] and hydrogenated diphenylmethane diisocyanate (hydrogenated MDI, 4,4′-dicyclohexylmethane diisocyanate) 30.14 parts by mass And 0.01 part by weight of dibutyltin dilaurate (DBTDL) and 200.0 parts by weight of acryloylmorpholine (“NK Ester A-MO” manufactured by Shin-Nakamura Chemical Co., Ltd.) were weighed into a 1 liter three-necked flask and stirred and mixed. Then, a urethane prepolymer having isocyanate groups at both ends of the molecular chain was synthesized by reacting at 80 ° C. for 4 hours.

  Next, 0.84 parts by mass of 2-hydroxyethyl acrylate (2-HEA) is added to 100 parts by mass of the urethane prepolymer, and the mixture is reacted at 80 ° C. for 4 hours with stirring and mixing. 2) was synthesized. It was 22500 when the number average molecular weight of the obtained urethane acrylate oligomer (A-2) was measured by GPC.

  Next, 100.0 parts by mass of the urethane acrylate oligomer (A-2) (containing 60% by mass of acryloylmorpholine) and 1.0 part by mass of a photopolymerization initiator “Irgacure 184D” manufactured by Ciba Specialty Chemicals Co., Ltd. After stirring and mixing, vacuum-defoaming was performed to prepare a UV curable adhesive resin composition.

  Next, using the adhesive resin composition, a peel strength measurement sample was prepared in the same manner as in Example 1, and the peel strength was measured. (1) When the adherend was a gold-treated film, the peel strength was measured. The strength is 389 N / m. (2) When the adherend is an IZO-treated PET film, the peel strength is 684 N / m, which has a high peel strength for any adherend. I found out.

  Further, using the adhesive resin composition, a glass transition temperature measurement sample was prepared in the same manner as in Example 1, and the glass transition temperature was measured. As a result, it was 172 ° C., which was sufficient as an adhesive material for electronic components. It was found to have a glass transition temperature.

In addition, the repeating number (n) of the urethane prepolymer part of the urethane acrylate oligomer (A-2) used in the UV curable adhesive resin composition is the number average molecular weight 22500 of the urethane acrylate oligomer and the number average molecular weight of the polycarbonate diol. Calculation using 1180, molecular weight of polyisocyanate (hydrogenated MDI) 258.314, molecular weight of acrylate chain (2-HEA) 116.11,
(22500-2 × 116.11-258.314) / (1180 + 258.314) = 15.3
Met.

(Comparative Example 1)
100.0 parts by mass of a polyether polyol obtained by polymerizing propylene oxide with propylene glycol and having a number average molecular weight of 930, 25.89 parts by mass of isophorone diisocyanate (IPDI), and 0.01 parts by mass of dibutyltin dilaurate (DBTDL) A urethane prepolymer having isocyanate groups at both ends of the molecular chain was synthesized by weighing into a 1 liter three-necked flask and reacting at 80 ° C. for 4 hours with stirring and mixing.

  Next, 3.1 parts by mass of 2-hydroxyethyl acrylate (2-HEA) is added to 100 parts by mass of the urethane prepolymer, and the mixture is reacted at 80 ° C. for 4 hours with stirring and mixing. 3) was synthesized. It was 17600 when the number average molecular weight of the obtained urethane acrylate oligomer (A-3) was measured by GPC.

  Next, 60.0 parts by mass of the urethane acrylate oligomer (A-3), 40.0 parts by mass of acryloylmorpholine (“NK Ester A-MO” manufactured by Shin-Nakamura Chemical Co., Ltd.), and Ciba Specialty Chemicals Co., Ltd. A photopolymerization initiator “Irgacure 184D” 1.0 part by mass was stirred and mixed, and then vacuum degassed to prepare a UV curable adhesive resin composition.

  Next, using the adhesive resin composition, a peel strength measurement sample was prepared in the same manner as in Example 1, and the peel strength was measured. (1) When the adherend was a gold-treated film, the peel strength was measured. The strength is 1494 N / m. (2) When the adherend is an IZO-treated PET film, the peel strength is 985 N / m, which has a high peel strength for any adherend. I found out.

  Further, using the above adhesive resin composition, a glass transition temperature measurement sample was prepared in the same manner as in Example 1, and the glass transition temperature was measured. As a result, it was -25 ° C., and the glass transition temperature was too low. It was found to be insufficient as an adhesive material for electronic components.

In addition, the repeating number (n) of the urethane prepolymer part of the urethane acrylate oligomer (A-3) used in the UV curable adhesive resin composition is the number average molecular weight of the urethane acrylate oligomer of 17600 and the number average of the polyether polyol. When calculated using a molecular weight of 930, a polyisocyanate (IPDI) molecular weight of 222.28, and an acrylate chain (2-HEA) molecular weight of 116.11,
(17600−2 × 116.11−222.28) / (930 + 222.28) = 14.9
Met.

(Comparative Example 2)
100.0 parts by mass of a polyether polyol having a bifunctional and number average molecular weight of 360 obtained by polymerizing propylene oxide to propylene glycol, 60.8 parts by mass of isophorone diisocyanate (IPDI), 0.01 parts by mass of dibutyltin dilaurate (DBTDL), 108.6 parts by mass of acryloylmorpholine (“NK Ester A-MO” manufactured by Shin-Nakamura Chemical Co., Ltd.) is weighed into a 1 liter three-necked flask and reacted at 80 ° C. for 4 hours with stirring and mixing. A urethane prepolymer having isocyanate groups at both ends was synthesized.

  Next, 2.14 parts by mass of 2-hydroxyethyl acrylate (2-HEA) is added to 100 parts by mass of the urethane prepolymer, and the mixture is reacted at 80 ° C. for 4 hours with stirring and mixing. 4) was synthesized. It was 5200 when the number average molecular weight of the obtained urethane acrylate oligomer (A-4) was measured by GPC.

  Next, 100.0 parts by mass of the urethane acrylate oligomer (A-4) (containing 40% by mass of acryloylmorpholine) and 1.0 part by mass of a photopolymerization initiator “Irgacure 184D” manufactured by Ciba Specialty Chemicals Co., Ltd. After stirring and mixing, vacuum-defoaming was performed to prepare a UV curable adhesive resin composition.

  Next, using the adhesive resin composition, a peel strength measurement sample was prepared in the same manner as in Example 1, and the peel strength was measured. (1) When the adherend was a gold-treated film, the peel strength was measured. The strength is 43 N / m. (2) When the adherend is an IZO-treated PET film, the peel strength is 25 N / m, which has a low peel strength for any adherend. I found out.

  Moreover, when the glass transition temperature measurement sample was produced using the adhesive resin composition in the same manner as in Example 1 and the glass transition temperature was measured, it was 96 ° C. and was sufficient as an adhesive material for electronic components. It was found to have a glass transition temperature.

In addition, the repeating number (n) of the urethane prepolymer part of the urethane acrylate oligomer (A-4) used in the UV curable adhesive resin composition is the number average molecular weight of the urethane acrylate oligomer of 5200, the number average of the polyether polyol. When calculated using a molecular weight of 360, a polyisocyanate (IPDI) molecular weight of 222.28, and an acrylate chain (2-HEA) molecular weight of 116.11,
(5200−2 × 116.11−222.28) / (360 + 222.28) = 8.1
Met.

(Comparative Example 3)
Bifunctional polycarbonate diol having a number average molecular weight of 2600 [Nipporan 980R manufactured by Nippon Polyurethane Industry Co., Ltd.] 100.0 parts by mass, isophorone diisocyanate (IPDI) 15.00 parts by mass, dibutyltin dilaurate (DBTDL) 0.01 parts by mass, acryloylmorpholine (“Nikester A-MO” manufactured by Shin-Nakamura Chemical Co., Ltd.) 215.0 parts by weight was weighed into a 1-liter three-necked flask and allowed to react at 80 ° C. for 4 hours with stirring and mixing. A urethane prepolymer having an isocyanate group at the end was synthesized.

  Next, 0.84 parts by mass of 2-hydroxyethyl acrylate (2-HEA) is added to 100 parts by mass of the urethane prepolymer, and the mixture is reacted at 80 ° C. for 4 hours with stirring and mixing. 5) was synthesized. It was 18500 when the number average molecular weight of the obtained urethane acrylate oligomer (A-5) was measured by GPC.

  Next, 100.0 parts by mass of the urethane acrylate oligomer (A-5) (containing 65% by mass of acryloylmorpholine) and 1.0 part by mass of a photopolymerization initiator “Irgacure 184D” manufactured by Ciba Specialty Chemicals Co., Ltd. After stirring and mixing, vacuum-defoaming was performed to prepare a UV curable adhesive resin composition.

  Next, using the adhesive resin composition, a peel strength measurement sample was prepared in the same manner as in Example 1, and the peel strength was measured. (1) When the adherend was a gold-treated film, the peel strength was measured. The strength is 173 N / m. (2) When the adherend is an IZO-treated PET film, the peel strength is 219 N / m, which has a low peel strength for any adherend. I found out.

  Moreover, when the glass transition temperature measurement sample was produced using the adhesive resin composition in the same manner as in Example 1 and the glass transition temperature was measured, it was 168 ° C., which was sufficient as an adhesive material for electronic components. It was found to have a glass transition temperature.

In addition, the repeating number (n) of the urethane prepolymer part of the urethane acrylate oligomer (A-5) used in the UV curable adhesive resin composition is the number average molecular weight of the urethane acrylate oligomer 18500 and the number average molecular weight of the polycarbonate diol. Calculation using 2600, molecular weight of polyisocyanate (IPDI) 222.28, molecular weight of acrylate chain (2-HEA) 116.11,
(18500−2 × 116.11−222.28) / (2600 + 222.28) = 6.4
Met.

  From the above results, a urethane (meth) acrylate oligomer (A) having a urethane prepolymer portion composed of polycarbonate diol and polyisocyanate, wherein the urethane prepolymer portion has a repeating number (n) of 10 to 30, and (meth) It can be seen that the adhesive resin compositions of Examples containing a cyclic monomer having an acryloyl group are excellent in adhesion to metal oxides such as IZO and metals such as gold and have a high glass transition temperature after curing.

  On the other hand, the adhesive resin of Comparative Example 1 using a urethane (meth) acrylate oligomer containing a urethane prepolymer portion composed of a polyether polyol and a polyisocyanate and having a repeating number (n) of the urethane prepolymer portion of 10 to 30 Although the composition was excellent in adhesion to metal oxides such as IZO and metals such as gold, the glass transition temperature after curing was low.

  Moreover, the adhesive resin composition of the comparative example 2 using the urethane prepolymer part which consists of polyether polyol and polyisocyanate, and the repeating number (n) of this urethane prepolymer part is less than ten. Although the product had a high glass transition temperature after curing, it had very low adhesion to metal oxides such as IZO and metals such as gold.

  Further, the adhesive resin composition of Comparative Example 3 using a urethane (meth) acrylate oligomer having a urethane prepolymer portion composed of a polycarbonate diol and a polyisocyanate, but having a repeating number (n) of the urethane prepolymer portion of less than 10. Although the product had a high glass transition temperature after curing, it had low adhesion to metal oxides such as IZO and metals such as gold.

Claims (7)

A photocurable or electron beam curable adhesive resin composition comprising a bifunctional urethane (meth) acrylate oligomer (A) and a monomer component (B),
The urethane (meth) acrylate oligomer (A) includes a urethane prepolymer part composed of polycarbonate diol and polyisocyanate, and the number of repetitions (n) of the urethane prepolymer part is 10 to 30,
The adhesive resin composition, wherein the monomer component (B) includes a cyclic monomer having a (meth) acryloyl group.   The adhesive resin composition according to claim 1, wherein the number average molecular weight of the polycarbonate diol used for forming the urethane prepolymer part of the urethane (meth) acrylate oligomer (A) is 500 to 4000.   The adhesive resin composition according to claim 1, wherein the cyclic monomer having a (meth) acryloyl group is acryloylmorpholine.   The proportion of the urethane (meth) acrylate oligomer (A) in the total blending amount of the urethane (meth) acrylate oligomer (A) and the monomer component (B) is 10 to 80% by mass and the (meth) acryloyl group 2. The adhesive resin composition according to claim 1, wherein the ratio of the cyclic monomer having a content of 20 to 90% by mass.   The adhesive resin composition according to claim 1, wherein the polyisocyanate is hydrogenated diphenylmethane diisocyanate or isophorone diisocyanate.   Furthermore, a photoinitiator (C) is included, The adhesive resin composition of Claim 1 characterized by the above-mentioned.   The adhesive resin composition according to any one of claims 1 to 6, which is cured by irradiation with light or electron beam, has a glass transition temperature (Tg) of 80 ° C or higher, and a peel strength against gold and IZO of 300 N / An adhesive resin characterized by being m or more.