JP2010138361A - Hardenable resin composition and film-shaped adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hardenable resin composition and a film adhesive which hold a firm adhesive strength at the time of use, and can be simply peeled when a trouble generates. <P>SOLUTION: The hardenable resin composition includes (A) a resin which has a urethane bond, (B) a photopolymerizable compound which has an ethylenically unsaturated group, (C) a photoinitiator, (D) an epoxy resin, and (E) an epoxy resin curing agent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a curable resin composition and a film adhesive.

  As various electronic components become higher performance, smaller, lighter, and highly integrated, the number of semiconductor elements mounted on one substrate is increasing, and the price of the substrate is rising. Conventionally, high adhesiveness is required for an adhesive used for a substrate, and many thermosetting adhesives are used. However, thermosetting adhesives are difficult to peel off after curing, so if a problem occurs with a part or substrate that has been bonded once, the entire substrate must be discarded and can be recovered and reused. difficult.

On the other hand, as a peelable adhesive, for example, Patent Document 1 discloses a heat-peelable pressure-sensitive adhesive sheet whose adhesive strength is reduced by heating.
Japanese Patent No. 3766304

  However, the heat-peelable pressure-sensitive adhesive sheet described in Patent Document 1 is used for temporarily fixing a component and can be repeatedly fixed and peeled, but the adhesiveness during heating is not sufficient, It is difficult to use in applications that require high adhesion.

  The present invention has been made in view of the above circumstances. A curable resin composition and a film-like adhesive that can maintain a strong adhesive force during use and can be easily peeled off when a failure occurs. The purpose is to provide.

  As a result of intensive studies to achieve the above object, the present inventors have developed a strong adhesive force by curing the thermosetting component at the time of thermocompression bonding, and when exposed to actinic rays such as ultraviolet rays, The present inventors have found that it is effective to use a resin composition having two kinds of curability that lowers the adhesive force by curing, and has completed the present invention.

  That is, the present invention provides (A) a resin having a urethane bond, (B) a photopolymerizable compound having an ethylenically unsaturated group, (C) a photopolymerization initiator, (D) an epoxy resin, and (E) an epoxy resin. A curable resin composition containing a curing agent is provided.

  According to such a resin composition, by having the above-described structure, when it is irradiated with actinic rays such as ultraviolet rays after bonding while exhibiting excellent adhesiveness with various substrates by thermocompression bonding, the photocuring proceeds and the adhesiveness decreases. Therefore, it can be easily peeled from the substrate.

［式（１）中、Ｒは炭素数１〜１８のアルキレン基を示し、Ｘは２価の有機基を示し、ｍ及びｎはそれぞれ独立に１〜３０の整数を示す。なお、複数存在するＲはそれぞれ同一でも異なっていてもよい。また、ｎが２以上の場合、複数存在するＸ及びｍはそれぞれ同一でも異なっていてもよい。］ In the curable resin composition of the present invention, from the viewpoint of improving solubility in an organic solvent and flexibility, the resin (A) having a urethane bond is a resin having a structure represented by the following general formula (1). It is preferable that

[In Formula (1), R shows a C1-C18 alkylene group, X shows a bivalent organic group, and m and n show the integer of 1-30 each independently. A plurality of R may be the same or different. When n is 2 or more, a plurality of X and m may be the same or different. ]

  From the viewpoint of improving heat resistance and adhesiveness, the resin (A) having a urethane bond is preferably a resin having an amide bond and / or an imide bond. In addition, from the viewpoint of improving adhesiveness and peelability after photocuring, the resin (A) having a urethane bond is preferably a resin having a polybutadiene skeleton and / or a polyisoprene skeleton.

  Furthermore, in the curable resin composition of the present invention, the (B) photopolymerizable compound having an ethylenically unsaturated group contains a photopolymerizable compound having three or more ethylenically unsaturated groups in the molecule. It is preferable. Thereby, the peelability after photocuring can be further improved.

  The present invention also provides a film adhesive formed by forming the curable resin composition into a film. By forming the resin composition in the form of a film, it becomes easy to handle, maintains a strong adhesive force during use, and can be easily peeled off when a problem occurs.

  ADVANTAGE OF THE INVENTION According to this invention, the strong adhesive force is hold | maintained at the time of use, and when a malfunction generate | occur | produces, the curable resin composition and film adhesive which can be easily peeled can be provided.

  In this specification, “(meth) acrylate” means “acrylate” and “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” and “methacryl” corresponding thereto, and “(meth) acryloyl” means “acryloyl” and corresponding “methacryloyl”.

  The curable resin composition of the present invention comprises (A) a resin having a urethane bond (hereinafter, referred to as “(A) component”), (B) a photopolymerizable compound having an ethylenically unsaturated group (hereinafter, “case”). "(B) component"), (C) photopolymerization initiator (hereinafter referred to as "(C) component"), (D) epoxy resin (hereinafter, sometimes referred to as "(D) component"), and (E) An epoxy resin curing agent (hereinafter referred to as “component (E)” in some cases) is included. Hereinafter, each component will be described in detail.

<(A) component: resin having a urethane bond>
(A) As resin which has a urethane bond, since it is excellent in adhesiveness with a board | substrate, for example, a polyurethane resin, a polyimide resin having a urethane skeleton, a polyamideimide resin having a urethane skeleton, a polyamide resin having a urethane skeleton, etc. And a resin having a urethane skeleton and an amide bond or an imide bond. These can be used individually by 1 type or in combination of 2 or more types.

  In the present invention, resins having a urethane bond that can be used as the component (A) include, for example, polyether diols, polyester diols, polycaprolactone diols, polycarbonate diols, polybutadiene diols, polyisoprene diols, and the like. This diol compound is obtained by reacting with a compound having an isocyanate group.

  In particular, (A) the resin having a urethane bond in the molecule includes a polyurethane resin having a polycarbonate skeleton and / or an imide bond from the viewpoint of improving solubility in organic solvents, flexibility, heat resistance and adhesiveness. Is preferred.

［式（２）中、Ｒは炭素数１〜１８のアルキレン基を示し、ｍは１〜３０の整数を示す。］で表されるポリカーボネートジオール類と、下記一般式（３）；
ＯＣＮ−Ｘ−ＮＣＯ （３）
［式（３）中、Ｘは２価の有機基を示す。］で表されるジイソシアネート類とを反応させることにより得られる。 Examples of the urethane resin having a polycarbonate skeleton include the following general formula (2);

[In Formula (2), R shows a C1-C18 alkylene group, m shows the integer of 1-30. A polycarbonate diol represented by the following general formula (3);
OCN-X-NCO (3)
[In formula (3), X represents a divalent organic group. It is obtained by reacting with a diisocyanate represented by the formula:

［式（１）中、Ｒは炭素数１〜１８のアルキレン基を示し、Ｘは２価の有機基を示し、ｍ及びｎはそれぞれ独立に１〜３０の整数を示す。なお、複数存在するＲはそれぞれ同一でも異なっていてもよい。また、ｎが２以上の場合、複数存在するＸ及びｍはそれぞれ同一でも異なっていてもよい。］ The urethane resin having a polycarbonate skeleton thus obtained has a structure represented by the following general formula (1).

[In Formula (1), R shows a C1-C18 alkylene group, X shows a bivalent organic group, and m and n show the integer of 1-30 each independently. A plurality of R may be the same or different. When n is 2 or more, a plurality of X and m may be the same or different. ]

  Examples of the divalent organic group represented by X in the general formulas (1) and (3) include an alkylene group having 1 to 20 carbon atoms and an unsubstituted or methyl group having 1 to 5 carbon atoms such as a methyl group. And an arylene group such as a phenylene group substituted with a lower alkyl group. The number of carbon atoms of the alkylene group is more preferably 1-18. Examples of the divalent organic group represented by X include fragrances such as diphenylmethane-4,4′-diyl group, hydrogenated diphenylmethane-4,4′-diyl group, and diphenylsulfone-4,4′-diyl group. A group having two rings is preferred.

  Examples of the polycarbonate diol represented by the general formula (2) include α, ω-poly (hexamethylene carbonate) diol and α, ω-poly (3-methyl-pentamethylene carbonate) diol, which are commercially available. Examples of such products include PLACEL CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, 220HL (trade name) manufactured by Daicel Chemical Industries, Ltd., and PCDL T-5651, T5652 manufactured by Asahi Kasei Chemicals Corporation. T-6001, T6002 (brand name), etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

  Moreover, it is preferable to use together the polycarbonate diol represented by the said General formula (2), and the diol compound which has a double bond in a molecule | numerator like polybutadiene diols or polyisoprene diols. Urethane resin prepared using polybutadiene diols or polyisoprene diols can reduce the adhesive strength by improving the cross-linking density with component (B) described later when irradiated with actinic rays. It can be easily peeled off when a failure occurs in the part or board.

  Polybutadiene diols or polyisoprene diols include compounds having “1,4-repeat units” or “1,2-repeat units”.

Here, in the polybutadiene skeleton of polybutadiene diols, “1,4-repeating unit” is a repeating unit represented by the following chemical formula (1t) or (1c), and “1,2-repeating unit” Is a repeating unit represented by the following chemical formula (1d).

［式（２Ａ）中、ｎは１〜６０の整数を示す。］ Examples of butadiene diols mainly having 1,4-repeating units include Poly bd R-45HT and Poly bd R-15HT (trade name, manufactured by Idemitsu Kosan Co., Ltd.). Examples of the polybutadiene diols mainly having 1,2-repeating units include compounds represented by the following general formula (2A). Specific examples include G-1000, G-2000, G-3000 (Nippon Soda). Company name, product name). Examples of polyisoprene diols mainly having 1,2-repeat units include Poly IP (trade name, manufactured by Idemitsu Kosan Co., Ltd.).

[In formula (2A), n shows the integer of 1-60. ]

  In particular, considering the solubility of the produced resin (A) having a urethane bond in an organic solvent, polybutadiene diols or polyisoprene diols having a branched skeleton are preferable, and as such polybutadiene diols or polyisoprene diols, Polybutadiene diol and polyisoprene diol mainly having 1,2-repeat units are preferable.

  Also, diol compounds other than polycarbonate diols, polybutadiene diols and polyisoprene diols can be used in combination. Examples of diol compounds other than polycarbonate diols, polybutadiene diols, and polyisoprene diols include polyether diols, polyester diols, polycaprolactone diols, and silicone diols.

  Examples of the diisocyanates represented by the general formula (3) include diphenylmethane-2,4′-diisocyanate; 3,2′-, 3,3′-, 4,2′-, 4,3 ′. -, 5,2'-, 5,3'-, 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate; 3,2'-, 3,3'-, 4,2 '-, 4,3'-, 5,2'-, 5,3'-, 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate; 3,2'-, 3, 3'-, 4,2'-, 4,3'-, 5,2'-, 5,3'-, 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate; diphenylmethane -4,4'-diisocyanate; diphenylmethane-3,3'-diisocyanate; dipheny Diphenylmethane diisocyanate compounds such as methane-3,4′-diisocyanate and their hydrogenated products; diphenyl ether-4,4′-diisocyanate; benzophenone-4,4′-diisocyanate; diphenylsulfone-4,4′-diisocyanate; 2,4-diisocyanate; tolylene-2,6-diisocyanate; m-xylylene diisocyanate; p-xylylene diisocyanate; naphthalene-2,6-diisocyanate; 4,4 '-[2,2bis (4-phenoxyphenyl) Propane] diisocyanate. Like these diisocyanates, it is preferable to use an aromatic polyisocyanate in which X in the formula (3) is a group having an aromatic ring. These can be used alone or in combination of two or more.

  In addition, the diisocyanates represented by the general formula (3) include, within the scope of the object of the present invention, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane. Aliphatic or alicyclic isocyanates such as diisocyanate, transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, and lysine diisocyanate, or trifunctional or higher functional polyisocyanates can be used.

  The diisocyanates represented by the general formula (3) may be stabilized with a blocking agent necessary to avoid changes over time. Examples of the blocking agent include hydroxy acrylate, alcohol typified by methanol, phenol, oxime and the like, but there is no particular limitation.

  The blending ratio of the diol compound and the diisocyanate represented by the general formula (3) is appropriately adjusted depending on whether the terminal of the resin to be generated is a hydroxyl group or an isocyanate group. In addition, from the viewpoint that various skeletons can be easily introduced for enhancing the functionality of the polyurethane resin, the ratio of the number of hydroxyl groups to the number of isocyanate groups (isocyanate group / hydroxyl group number) can be adjusted to be 1.01 or more. preferable. By setting it as such a ratio, it becomes urethane resin (henceforth "compound (a-1)" depending on the case) where the terminal of resin is an isocyanate group, and can introduce | transduce various frame | skeleton easily.

  The reaction between the diol compound and the diisocyanate represented by the general formula (3) can be performed in the absence of a solvent or in the presence of an organic solvent. The reaction temperature is preferably 60 to 200 ° C, more preferably 80 to 180 ° C. The reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions employed, and the like. For example, it can be 2 to 5 hours on a flask scale of 1 to 5 L (liter).

  The number average molecular weight of the compound (a-1) thus obtained is preferably 500 to 30,000, more preferably 1,000 to 2,5000, and 1,500 to 20,000. It is particularly preferred that

  In the present specification, the number average molecular weight is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve. Further, the number average molecular weight, the weight average molecular weight, and the degree of dispersion are defined as follows.

(A) Number average molecular weight (Mn)
Mn = Σ (N _i M _i ) / Ni = ΣX _i M _i
(X _i = Mole fraction of molecules with molecular weight M _i = N _i / ΣN _i )
(B) Weight average molecular weight (Mw)
Mw = Σ (N _i M _i ² ) / ΣN _i M _i = ΣW _i M _i
(W _i = Molecular weight M _i molecular weight fraction = N _i M _i / ΣN _i M _i )
(C) Molecular weight distribution (dispersion degree)
Dispersity = Mw / Mn

  Various skeletons can be introduced into the component (A) using the compound (a-1) and a compound capable of reacting with an isocyanate group.

［式（４）中、Ｒは炭素数１〜１８のアルキレン基を示し、Ｘは２価の有機基を示し、ｍ及びｎはそれぞれ独立に１〜２０の整数を示す。なお、複数存在するＲ及びＸはそれぞれ同一でも異なっていてもよい。また、ｎが２以上の場合、複数存在するｍはそれぞれ同一でも異なっていてもよい。］ As a compound (a-1), the compound represented by following General formula (4) is mentioned, for example.

[In Formula (4), R shows a C1-C18 alkylene group, X shows a bivalent organic group, m and n show the integer of 1-20 each independently. A plurality of R and X may be the same or different. When n is 2 or more, a plurality of m may be the same or different. ]

  Examples of the compound capable of reacting with an isocyanate group include a monohydroxy compound, a trivalent polycarboxylic acid having an acid anhydride group and a derivative thereof, a tetravalent polycarboxylic acid having an acid anhydride group, and a compound having a carboxyl group. And dihydroxy compounds having a carboxyl group.

［式（５）及び（６）中、Ｒ’は、水素原子、炭素数１〜１０のアルキル基又はフェニル基を示し、Ｙ^１は、−ＣＨ_２−、−ＣＯ−、−ＳＯ_２−、又は−Ｏ−を示す。］ Although the trivalent polycarboxylic acid having an acid anhydride group and its derivative are not particularly limited, for example, a compound represented by the following general formula (5) or (6) can be used.

Wherein (5) and (6), R 'is a hydrogen atom, an alkyl group or a phenyl group having 1 to 10 carbon atoms, ^{Y 1} _{is, -CH 2 -, - CO -} , - SO 2 -, Or -O- is shown. ]

  As the trivalent polycarboxylic acid having an acid anhydride group, trimellitic anhydride is particularly preferable from the viewpoint of cost.

［式（７）中、Ｙ^２は、下記式（８）：

で示される複数の基から選ばれる一種を示す。］ Moreover, although it does not specifically limit about the tetravalent polycarboxylic acid which has the said acid anhydride group, For example, it is preferable to use the tetracarboxylic dianhydride represented by following General formula (7). These can be used alone or in combination of two or more.

[In formula (7), Y ² represents the following formula (8):

1 type selected from a plurality of groups represented by ]

  In addition to these, as necessary, an aliphatic dicarboxylic acid (succinic acid, glutaric acid, adipic acid, azelaic acid, suberic acid, sebacic acid, decanedioic acid, dodecanedioic acid, dimer acid, etc.) Aromatic dicarboxylic acids (isophthalic acid, terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, etc.) can be used in combination. In this case, an amide bond is also formed in the molecular chain.

  When the polyurethane resin having the polycarbonate skeleton is reacted with a trivalent polycarboxylic acid having an acid anhydride group and a derivative thereof, or a tetravalent polycarboxylic acid having an acid anhydride group, the compound is used as the isocyanate compound. A compound other than (a-1) (hereinafter referred to as “compound (a-2)”) can also be used. The compound (a-2) is not particularly limited as long as it is an isocyanate compound other than the compound (a-1). For example, diisocyanates represented by the above general formula (3), trivalent or higher polyisocyanates Etc. These can be used alone or in combination of two or more. The preferable range of the number average molecular weight of the isocyanate compound of the compound (a-2) is the same as that of the compound (a-1).

  Moreover, in this embodiment, an amine compound can also be used together with the said isocyanate compound. As an amine compound, the compound which converted the isocyanate group in the said isocyanate compound into the amino group is mentioned. Conversion of an isocyanate group to an amino group can be performed by a known method. The preferred range of the number average molecular weight of the amine compound is the same as that of the above compound (a-1).

  As compound (a-2), it is preferable that 50-100 mass% of the total amount is aromatic polyisocyanate, and considering the balance of solubility, mechanical properties, cost, etc., 4,4′-diphenylmethane Diisocyanate is particularly preferred.

  When the compound (a-1) and the compound (a-2) are used in combination, the equivalent ratio of the compound (a-1) / the compound (a-2) is 0.1 / 0.9 to 0.9 / 0. 1 is preferable, 0.2 / 0.8 to 0.8 / 0.2 is more preferable, and 0.3 / 0.7 to 0.7 / 0.3 is particularly preferable. . When the equivalent ratio is in this range, good adhesion to the substrate and step following ability can be obtained.

  In addition, the blending ratio of the trivalent polycarboxylic acid having acid anhydride groups or derivatives thereof and / or the tetravalent polycarboxylic acid having acid anhydride groups is a carboxyl group relative to the total number of isocyanate groups in the isocyanate. The ratio of the total number of acid anhydride groups (total number of carboxyl groups and acid anhydride groups / total number of isocyanate groups) is preferably 0.6 to 1.4, preferably 0.7 to 1.3. It is more preferable to set it as 0.8, and it is especially preferable to set it as 0.8-1.2. If this ratio is less than 0.6 or exceeds 1.4, it tends to be difficult to increase the molecular weight of the resin containing polyimide bonds, and the target characteristics may not be obtained.

［式中、Ｒは炭素数１〜１８のアルキレン基を示し、Ｘは２価の有機基を示し、ｍ及びｎはそれぞれ独立に１〜３０の整数を示す。なお、複数存在するＲ及びＸはそれぞれ同一でも異なっていてもよい。また、ｎが２以上の場合、複数存在するｍはそれぞれ同一でも異なっていてもよい。］
で表される繰り返し単位を含むアミドイミド結合を有するポリウレタン樹脂を得ることができる。 In addition, when the compound represented by the general formula (5) and the compound represented by the general formula (4) are used, the following general formula (9);

[Wherein, R represents an alkylene group having 1 to 18 carbon atoms, X represents a divalent organic group, and m and n each independently represents an integer of 1 to 30. A plurality of R and X may be the same or different. When n is 2 or more, a plurality of m may be the same or different. ]
The polyurethane resin which has an amide imide bond containing the repeating unit represented by this can be obtained.

［式中、Ｒは炭素数１〜１８のアルキレン基を示し、Ｘは２価の有機基を示し、Ｙ^１は、−ＣＨ_２−、−ＣＯ−、−ＳＯ_２−、又は−Ｏ−を示し、ｍ及びｎはそれぞれ独立に１〜３０の整数を示す。なお、複数存在するＲ及びＸはそれぞれ同一でも異なっていてもよい。また、ｎが２以上の場合、複数存在するｍはそれぞれ同一でも異なっていてもよい。］
で表される繰り返し単位を含むアミドイミド結合を有するポリウレタン樹脂を得ることができる。 When the compound represented by the general formula (6) and the compound represented by the general formula (4) are used, the following general formula (10);

[Wherein, R represents an alkylene group having 1 to 18 carbon atoms, X represents a divalent organic group, and Y ¹ represents —CH ₂ —, —CO—, —SO ₂ —, or —O—. M and n each independently represent an integer of 1 to 30. A plurality of R and X may be the same or different. When n is 2 or more, a plurality of m may be the same or different. ]
The polyurethane resin which has an amide imide bond containing the repeating unit represented by this can be obtained.

［式中、Ｒは炭素数１〜１８のアルキレン基を示し、Ｘは２価の有機基を示し、Ｙ^２は、上記式（８）で示される複数の基から選ばれる基を示し、ｍ及びｎはそれぞれ独立に１〜３０の整数を示す。なお、複数存在するＲ及びＸはそれぞれ同一でも異なっていてもよい。また、ｎが２以上の場合、複数存在するｍはそれぞれ同一でも異なっていてもよい。］
で示される繰り返し単位を含むイミド結合を有するポリウレタン樹脂を得ることができる。 When the compound represented by the general formula (7) and the compound represented by the general formula (4) are used, the following general formula (11);

[Wherein, R represents an alkylene group having 1 to 18 carbon atoms, X represents a divalent organic group, Y ² represents a group selected from a plurality of groups represented by the above formula (8), m And n each independently represents an integer of 1 to 30. A plurality of R and X may be the same or different. When n is 2 or more, a plurality of m may be the same or different. ]
The polyurethane resin which has an imide bond containing the repeating unit shown by can be obtained.

  In the present invention, a trivalent polycarboxylic acid having an acid anhydride group and a derivative thereof, and a tetravalent poly having an acid anhydride group in the process for producing a “resin having a urethane bond” used as the component (A). In the reaction of one or more compounds selected from carboxylic acids with an isocyanate compound or an amine compound, carbon dioxide gas generated free is removed from the reaction system in the presence of an organic solvent, preferably a non-nitrogen-containing polar solvent. It can be carried out by heat condensation while heating.

［式（１２）中、Ｒ^１は水素原子又は炭素数１〜３のアルキル基を示す］ In the present invention, examples of other resins having a urethane bond that can be used as the component (A) include compounds represented by the above general formulas (2) and (3) and the following general formula (12), respectively. And a resin obtained by reacting under the same conditions as in the synthesis of the compound (a-1) can be used.

[In Formula (12), R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms]

  Examples of the compound represented by the general formula (12) include dimethylolpropionic acid and dimethylolbutanoic acid.

［式（１３）中、Ｒは、炭素数１〜１８のアルキレン基を示し、Ｒ^１は、水素原子又は、炭素数１〜３のアルキル基を示し、Ｘは２価の有機基を示し、ｍ及びｎはそれぞれ独立に１〜３０の整数を示す。なお、複数存在するＲ及びＸはそれぞれ同一でも異なっていてもよい。また、ｎが２以上の場合、複数存在するｍはそれぞれ同一でも異なっていてもよい。］ The resin thus obtained is a urethane resin having a carboxyl group containing a repeating structure represented by the following general formula (13), and improves the reactivity with an epoxy resin which is a component (D) described later. Can do.

[In the formula (13), R represents an alkylene group having 1 to 18 carbon atoms, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X represents a divalent organic group, m and n each independently represents an integer of 1 to 30. A plurality of R and X may be the same or different. When n is 2 or more, a plurality of m may be the same or different. ]

  When the urethane resin having a carboxyl group obtained as described above has an isocyanate residue, the isocyanate residue may be reacted with an acid anhydride, an alcohol, a lactam, an oxime, or the like.

  Moreover, the photopolymerizable unsaturated group is introduced into the urethane resin having a carboxyl group containing the repeating structure represented by the general formula (13) by modifying part or all of the carboxyl group. Can do. As a result, it can function as a photo-curable component when irradiated with actinic rays such as ultraviolet rays, and is photocrosslinked with the photopolymerizable compound having an ethylenically unsaturated group as the component (B) to bond the adhesive layer. The peelability can be further improved by reducing the force. The unsaturated group can be introduced, for example, by reacting 2-hydroxyethyl (meth) acrylate or the like.

  Examples of the non-nitrogen-containing polar solvent include ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether; sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, and sulfolane; Examples thereof include ester solvents such as γ-butyrolactone and cellosolve acetate; ketone solvents such as cyclohexanone and methyl ethyl ketone; and aromatic hydrocarbon solvents such as toluene and xylene. These can be used alone or in combination of two or more.

  Among the above solvents, it is preferable to select and use a solvent that can dissolve the resin to be formed. Moreover, it is preferable to use what is suitable as a solvent of curable resin composition as it is after a synthesis | combination. Among the above solvents, γ-butyrolactone is most preferable for highly volatile and efficient reaction in a homogeneous system.

  Moreover, it is preferable that the usage-amount of a solvent shall be 0.8-5.0 times (mass ratio) of resin which has the urethane bond to produce | generate. If this amount is less than 0.8 times, the viscosity at the time of synthesis tends to be too high and the synthesis tends to be difficult due to the inability to stir, and if it exceeds 5.0 times, the reaction rate tends to decrease.

  The reaction temperature is preferably 80 to 210 ° C, more preferably 100 to 190 ° C, and particularly preferably 120 to 180 ° C. If this temperature is less than 80 ° C., the reaction time tends to be too long, and if it exceeds 210 ° C., a three-dimensional reaction occurs during the reaction and gelation tends to occur. The reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed.

  If necessary, the reaction may be performed in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.

  Further, after the synthesis is completed, the isocyanate group at the resin terminal can be blocked with a blocking agent of alcohols, lactams, oximes, carboxylic acids, or acid anhydrides.

  The number average molecular weight of the resin having a urethane bond thus obtained is preferably 10,000 to 65,000, more preferably 15,000 to 60,000, and 20,000 to 55. Is particularly preferred. If the number average molecular weight is less than 10,000, the peelability after photocuring tends to decrease, and if the number average molecular weight exceeds 65,000, it becomes difficult to dissolve in a non-nitrogen-containing polar solvent, There is a tendency to be insolubilized easily, and the workability tends to be inferior.

  As the resin of component (A) used in the resin composition of the present invention, two or more kinds of resins having different number average molecular weights may be mixed and used. At this time, it is preferable that the number average molecular weight measured by GPC method is within the above range for all of the two or more resins to be mixed. The mixing ratio when mixing two or more resins having different number average molecular weights is not particularly limited. Further, the concentration of the resin solution can be selected without limitation.

<(B) component: a photopolymerizable compound having one or more unsaturated groups in the molecule>
(B) As a photopolymerizable compound having one or more unsaturated groups in the molecule, for example, a bisphenol A (meth) acrylate compound; obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid Compounds obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid; urethane monomers or urethane oligomers such as (meth) acrylate compounds having a urethane bond, and having a urethane bond (meta ) Urethane monomers or urethane oligomers such as acrylate compounds, in addition to these, nonylphenoxy polyoxyethylene acrylate; γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β -Hydroxyalkyl-β '-(meth) acryloyloxy Phthalic acid compounds such as alkyl -o- phthalate; (meth) acrylic acid alkyl esters, EO-modified nonylphenyl (meth) acrylate or the like can be exemplified. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of bisphenol A-based (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy). ) Phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane. It is done.

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy nonaethoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ( (Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxyhexa) Decaethoxy) phenyl) propane. Of these, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as BPE-500 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). 4- (Methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). These can be used individually by 1 type or in combination of 2 or more types.

  Examples of 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic) Xinonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) propane 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane and 2,2-bis (4-((meth)) Acryloxyhexadecapropoxy) phenyl) propane. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane, Examples include 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol include 2 to 14 polyethylene glycol di (meth) acrylate propylene groups having 2 to 14 ethylene groups. Polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, trimethylol Propane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, EO / PO modified trimethylolpropane tri (meth) acrylate, tetramethylol methanetri (meth) acrylate Examples include relate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These can be used individually by 1 type or in combination of 2 or more types.

“EO” refers to “ethylene oxide”, and “PO” refers to “propylene oxide”. “EO modified” means having a block structure of ethylene oxide units (—CH ₂ CH ₂ O—), and “PO modified” means propylene oxide units (—CH ₂ CH (CH ₃ ) O—). It means having a block structure.

  Examples of the compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include trimethylolpropane triglycidyl ether tri (meth) acrylate and 2,2-bis (4- (meth) acryloxy- An epoxy acrylate compound obtained by reacting an epoxy resin such as 2-hydroxy-propyloxy) phenyl, a novolak-type epoxy resin, a bisphenol-type epoxy resin, or a salicylaldehyde-type epoxy resin with (meth) acrylic acid. Examples of the α, β-unsaturated carboxylic acid include (meth) acrylic acid. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the urethane monomer or urethane oligomer include (meth) acrylic monomers having an OH group at the β-position, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Addition reaction product with diisocyanate compound; tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate; EO modified urethane di (meth) acrylate; EO or PO modified urethane di (meth) acrylate; carboxyl group-containing urethane (meta ) Acrylate; (meth) acrylic monomer having OH group at β-position, diisocyanate compound, polyether diol, polyester diol, polycaprolactone diol Addition reaction products with silicone diols; polyfunctional (meth) acrylate compounds having a hydroxyl group such as pentaerythritol tri (meth) acrylate and dipentaerythritol pentaacrylate, polymethylene diisocyanate such as hexamethylene diisocyanate, tolylene diisocyanate, etc. And an addition reaction product with a diisocyanate compound such as cycloalkylene diisocyanate such as arylene diisocyanate and isophorone diisocyanate.

  The component (B) of the present invention preferably contains a compound having three or more ethylenically unsaturated groups in the molecule from the viewpoint of further improving the peelability of the photocured film after irradiation with actinic rays. More preferably, it contains a compound having 5 or more ethylenically unsaturated groups, and particularly preferably contains a compound having 6 or more ethylenically unsaturated groups in the molecule. From the viewpoint of storage stability, the number of ethylenically unsaturated groups in the molecule is preferably 20 or less. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the compound having three or more ethylenically unsaturated groups in the molecule include trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO・ PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, pentaerythritol Polyfunctional (meth) acrylate compounds having a hydroxyl group such as tri (meth) acrylate and dipentaerythritol pentaacrylate and polyethylene such as hexamethylene diisocyanate Addition reaction products with diisocyanate compounds such as arylene diisocyanates such as diisocyanate and tolylene diisocyanate, cycloalkylene diisocyanates such as isophorone diisocyanate, epoxy resins such as novolac type epoxy resins, bisphenol type epoxy resins, salicylaldehyde type epoxy resins and (meth) The epoxy acrylate compound obtained by making it react with acrylic acid is mentioned.

［式（１４）中、Ｒは、炭素数１〜１８のアルキレン基を示し、Ｒ^２は、水素原子又はメチル基を示し、Ｘは、２価の有機基を示し、Ｚは、２〜６価の有機基を示し、ｍ及びｎはそれぞれ独立に１〜３０の整数を示し、ｐ及びｑはそれぞれ独立に１〜５の整数を示す。なお、複数存在するＲ、Ｒ^２、Ｘ及びＹはそれぞれ同一でも異なっていてもよい。また、ｎが２以上の場合、複数存在するｍはそれぞれ同一でも異なっていてもよい。］ Moreover, the compound which has a polycarbonate skeleton from a viewpoint which can improve the adhesiveness before actinic light irradiation, a softness | flexibility, chemical resistance, and water resistance more. A compound having a polycarbonate skeleton has high crystallinity at room temperature, and crystallinity is lost and becomes amorphous at high temperature. They are thinking. Moreover, the compound which has a polycarbonate frame | skeleton considers that it is the factor which makes high adhesiveness also being excellent in compatibility with the urethane resin which is (A) component. Examples of the compound having a polycarbonate skeleton as the component (B) include a compound represented by the following general formula (14).

[In the formula (14), R represents an alkylene group having 1 to 18 carbon atoms, R ² represents a hydrogen atom or a methyl group, X represents a divalent organic group, and Z represents 2 to 6 A valent organic group, m and n each independently represent an integer of 1 to 30, and p and q each independently represents an integer of 1 to 5. A plurality of R, R ² , X and Y may be the same or different. When n is 2 or more, a plurality of m may be the same or different. ]

  The compound represented by the general formula (14) includes the diisocyanate compound represented by the general formula (4), 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meta). ) It can be obtained by reacting an ethylenically unsaturated group such as acrylate with a compound having a hydroxyl group.

［式（１５）中、Ｒは、炭素数１〜１８のアルキレン基を示し、Ｒ^２は、水素原子又はメチル基を示し、Ｘ及びＺは、それぞれ独立に２価の有機基を示し、ｍ及びｎはそれぞれ独立に１〜３０の整数を示す。なお、複数存在するＲ、Ｒ^２、Ｘ及びＹはそれぞれ同一でも異なっていてもよい。また、ｎが２以上の場合、複数存在するｍはそれぞれ同一でも異なっていてもよい。］ Among these (B) components, in particular, a compound having three or more ethylenically unsaturated groups and a polycarbonate skeleton in the molecule from the viewpoint of improving both the adhesiveness at the time of thermocompression bonding and the releasability after photocuring. Is preferably used. It is also preferable to use a compound having 3 or more ethylenically unsaturated groups in the molecule and a compound having 2 or less ethylenically unsaturated groups and a polycarbonate skeleton in the molecule. The compound having two or less ethylenically unsaturated groups and a polycarbonate skeleton in the molecule is represented by the following general formula (15) in which p and q are 1 in the compound represented by the general formula (14). Compounds.

[In the formula (15), R represents an alkylene group having 1 to 18 carbon atoms, R ² represents a hydrogen atom or a methyl group, X and Z each independently represent a divalent organic group, m And n each independently represents an integer of 1 to 30. A plurality of R, R ² , X and Y may be the same or different. When n is 2 or more, a plurality of m may be the same or different. ]

  When the above compound having 3 or more ethylenically unsaturated groups in the molecule and a compound having 2 or less ethylenically unsaturated groups and a polycarbonate skeleton in the molecule are used in combination, 3 or more in the molecule The content of the compound having an ethylenically unsaturated group is preferably 1 to 100 parts by mass, more preferably 5 to 30 parts by mass, and more preferably 10 to 25 parts per 100 parts by mass of the component (A). The part by mass is particularly preferred.

  Moreover, it is preferable that content of the compound which has 2 or less ethylenically unsaturated groups and polycarbonate frame | skeleton in a molecule | numerator is 5-100 mass parts with respect to 100 mass parts of (A) component, and 10-70. It is more preferable that it is a mass part, and it is especially preferable that it is 30-55 mass parts.

  The photopolymerizable compound as component (B) preferably has a number average molecular weight of 500 to 6,000, more preferably 1,000 to 5,000, and 1,500 to 5,000. It is particularly preferred. If the number average molecular weight is less than 500, the photocured film tends to be peeled off after the photocured film is peeled off. If the number average molecular weight exceeds 6,000, the adhesiveness before irradiation with actinic rays decreases, and photocuring Does not proceed sufficiently, and the peelability tends to decrease.

  Furthermore, examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic acid 2-ethylhexyl ester. . These can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (B) in the curable resin composition of the present invention is preferably 10 to 80 parts by mass and more preferably 20 to 70 parts by mass with respect to 100 parts by mass of the component (A). Preferably, it is 30-60 mass parts. When the content is less than 10 parts by mass, the photocurability becomes insufficient and the peelability tends to be lowered, and when it exceeds 80 parts by mass, the adhesiveness at the time of thermosetting tends to be lowered.

<(C) component: photopolymerization initiator>
Specific examples of the photopolymerization initiator include, for example, benzophenone, 4,4′-bis (dimethylamino) benzophenone (Michler ketone), 4,4′-bis (diethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone. 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-morpholinophenone) -butanone-1,2-ethylanthraquinone, Aromatic ketones such as phenanthrenequinone, quinones such as alkyl anthraquinone, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether, benzoins such as methyl benzoin and ethyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, - phenyl acridine, 1,7-bis (9,9'-acridinyl) acridine derivatives such as heptane, N- phenylglycine, N- phenylglycine derivatives, coumarin-based compounds. These can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (C) in the curable resin composition of the present invention is preferably 0.1 to 20 parts by mass, and 0.5 to 15 parts by mass with respect to 100 parts by mass of the component (B). It is preferably 1 to 10 parts by mass. When this content is less than 0.1 parts by mass, the photocuring is insufficient and the adhesive layer tends to be difficult to peel off, and when it exceeds 20 parts by mass, the surface of the adherend tends to be contaminated.

<(D) component: epoxy resin>
Although it does not specifically limit as an epoxy resin, Epoxy resins, such as a bisphenol A type, a bisphenol F type, a biphenyl type, an aliphatic alkyl type, a novolak type, can be used. Examples of the epoxy resin include bisphenol A type epoxy resin (trade name Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.), bisphenol F type epoxy resin (trade name YDF-170 manufactured by Toto Kasei Co., Ltd.), Phenol novolac type epoxy resin (trade name Epicoat 152, 154 of Yuka Shell Epoxy Co., Ltd .; trade name EPPN-201 manufactured by Nippon Kayaku Co., Ltd .; trade name DEN-438 manufactured by Dow Chemical Co., Ltd.), o -Cresol novolac type epoxy resins (trade names EOCN-125S, 103S, 104S, etc., manufactured by Nippon Kayaku Co., Ltd.), polyfunctional epoxy resins (trade names, Epon 1031S, manufactured by Yuka Shell Epoxy Co., Ltd .; Ciba Specialty Chemicals) Product name Araldite 0163 manufactured by Co., Ltd .; Product name Denacor manufactured by Nagase Kasei Co., Ltd. X-611, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-421, EX-411, EX-321, etc.), amine type epoxy resin (Oilized Shell Epoxy Co., Ltd.) Product name Epicoat 604; Product name YH434 manufactured by Tohto Kasei Co., Ltd. Product names TETRAD-X and TERRAD-C manufactured by Mitsubishi Gas Chemical Company, Inc. Product names GAN manufactured by Nippon Kayaku Co., Ltd .; Sumitomo Chemical (Trade name ELM-120 manufactured by Co., Ltd.), epoxy resin containing heterocyclic ring (trade name Araldite PT810 manufactured by Ciba Specialty Chemicals Co., Ltd.), alicyclic epoxy resin (ERL4234, 4299 manufactured by UCC) 4221, 4206, etc.), epoxidized polybudadiene obtained by partially epoxidizing polybutadiene (product PB-3600 manufactured by Daicel Chemical Industries, Ltd.) Nippon Soda Co., Ltd. trade name BF-1000, etc.), novolak type epoxy resins having a biphenyl skeleton, and aliphatic alkyl type epoxy resins, which can be used alone or in combination of two or more. Among these, those that are soluble in an organic solvent are preferable from the viewpoint of maintaining the transparency of the curable resin composition, and epoxidized polybudadiene obtained by partially epoxidizing polybutadiene is more preferable.

  The content of the component (D) in the curable resin composition of the present invention is preferably 1 to 200 parts by mass and more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the component (A). The amount is preferably 10 to 50 parts by mass. When the content is less than 1 part by mass, the thermosetting property becomes insufficient and the adhesiveness tends to decrease. When the content exceeds 200 parts by mass, the peelability of the adhesive layer from the adherend tends to decrease. There is.

<(E) component: epoxy resin curing agent>
Epoxy resin curing agents include imidazole, hydrazide, boron trifluoride-amine complexes, sulfonium salts, amine imides, polyamine salts, dicyandiamide, and these curing agents coated with polyurethane or polyester polymer materials. And microencapsulated. These can be used individually by 1 type or in combination of 2 or more types. Among these, in order to suppress thermal polymerization of the photopolymerizable compound at the time of epoxy resin thermal curing in the thermocompression bonding step, suppression of thermal polymerization of the epoxy resin by heating in the drying step when the curable resin composition is applied, The reaction start temperature is preferably 80 ° C to 150 ° C, more preferably 110 to 130 ° C. Examples of such epoxy resin curing agents include latent curing agents such as microcapsule type and heat dissolution type, and Novacure series (manufactured by Asahi Kasei Chemicals Co., Ltd.) as a typical product of microcapsule type A typical product of the mold is the Amicure series (manufactured by Ajinomoto Fine Techno).

  When the microcapsule type curing agent is heated to a predetermined temperature, the surrounding resin covering the curing agent is dissolved, the curing agent is diffused into the resin, and reaction with the epoxy resin is started. The heat-dissolving curing agent is a solid at room temperature, but dissolves when heated to a predetermined temperature and starts to react with the epoxy resin.

  The content of the component (E) in the curable resin composition of the present invention is preferably 0.1 to 200 parts by mass, and 1 to 150 parts by mass with respect to 100 parts by mass of the component (D). Is preferable, and it is especially preferable that it is 10-100 mass parts. When the content is less than 0.1 parts by mass, the thermosetting is insufficient and the adhesiveness of the adhesive layer tends to decrease. When the content exceeds 200 parts by mass, the surface of the adherend tends to be contaminated. .

<(F) component: filler>
The curable resin composition of the present invention can contain a filler (F) as necessary. There is no restriction | limiting in particular as a filler, For example, metal fillers, such as silver powder, gold powder, copper powder, nickel powder; Alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, oxidation Examples thereof include inorganic fillers such as calcium, magnesium oxide, aluminum oxide, aluminum nitride, crystalline silica, amorphous silica, boron nitride, titania, glass, iron oxide, and ceramics; and organic fillers such as carbon and rubber fillers. The shape of the filler is not particularly limited.

  The filler can be used properly according to the desired function. For example, the metal filler is added for the purpose of imparting electrical conductivity, thermal conductivity, thixotropy, etc. to the curable resin composition; the nonmetallic inorganic filler is thermally conductive, low thermal expansion, low hygroscopicity to the adhesive film. The organic filler is added for the purpose of imparting toughness to the adhesive film. These fillers can be used alone or in combination of two or more.

  Further, the curable resin composition of the present invention, if necessary, a plasticizer such as p-toluenesulfonic acid amide, a pigment, a filler, an antifoaming agent, a coupling agent, a stabilizer, an adhesion imparting agent, A leveling agent, a peeling accelerator, an antioxidant, a thermal crosslinking agent, and the like can be contained.

  Next, an adhesion method and a peeling method using the curable resin composition of the present invention will be described below.

(Adhesion method)
The solution of the curable resin composition can be used as an adhesive by applying or dropping the solution on the adherend to a desired thickness. Moreover, it can also be used as a film adhesive by shape | molding curable resin composition in a film form and affixing on a to-be-adhered body. The method and conditions for applying, dripping and pasting are not particularly limited.

  When the solution of the curable resin composition is used directly, it is preferable to dry the solvent at 60 to 120 ° C after application and dropping, and more preferably at 80 to 100 ° C. When it exceeds 120 ° C., it is thermally cured and the adhesiveness is lowered, and when it is 60 ° C. or lower, the solvent may not be completely dried and the adhesiveness may be lowered.

  Also when producing a film adhesive, it is preferable to process on said temperature conditions for the same reason.

  The thermocompression bonding is preferably performed at 80 to 200 ° C, more preferably 100 to 180 ° C. If it exceeds 200 ° C., thermal polymerization of the photocurable component may start and the adhesive strength may decrease, and if it is less than 80 ° C., the thermosetting of the curable resin composition does not proceed and the adhesive strength may decrease. There is sex.

  The pressure and time during thermocompression bonding can be arbitrarily adjusted by changing the components (D) and (E). The pressure bonding temperature needs to be a temperature at which thermosetting of the component (B) can be suppressed.

(Peeling method)
Next, the heat-cured adhesive layer is irradiated with actinic rays such as ultraviolet rays, and the adhesive layer after photocuring is peeled from the substrate by reducing the tackiness of the adhesive layer by photocuring.

  Here, as the light source of actinic light, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet rays is used. Moreover, what can radiate | emit visible light effectively, such as a flood bulb for photography, a solar lamp, can be used.

  According to the present embodiment, a substrate having no adhesive layer residue can be obtained by using a curable resin composition that can maintain a strong adhesive force during use and can be easily peeled off when a problem occurs. Can be recovered and reused.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not restrict | limited to this.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

(Synthesis example)
<Production of component (A-1)>
In a 3 L four-necked flask equipped with a stirrer, a condenser tube with an oil separator, a nitrogen inlet tube and a thermometer, 565.84 g of γ-butyrolactone, 1,6-hexanediol-based polycarbonate diol (manufactured by Daicel Chemical Industries, Ltd., product) Name “Placcel CD-220”) 695.04 g, 4,4′-diphenylmethane diisocyanate 105.0 g, and toluene diisocyanate 83.52 g were charged, heated to 150 ° C., and reacted at 150 ° C. for 4 hours.

  Next, 124.8 g of trimellitic anhydride was added to the reaction product and reacted at 70 ° C. for 3 hours. Subsequently, 75.0 g of 4,4′-diphenylmethane diisocyanate and 34.8 g of toluene diisocyanate were added again, and the mixture was reacted at 120 ° C. for 1 hour and at 180 ° C. for 3 hours. After the reaction, 563.9 g of methyl ethyl ketone was added and cooled, and 46.4 g of 2-hydroxyethyl acrylate was further added and reacted at 120 ° C. for 3 hours to give a resin having a number average molecular weight of 45,000 (polycarbonate-modified polyamideimide resin). : (A) component). The number average molecular weight was adjusted by collecting a small amount of the reaction solution every reaction time and observing the rate of change in viscosity with a Gardner bubble viscometer. The obtained resin was diluted with methyl ethyl ketone to obtain a polycarbonate-modified polyamideimide resin solution having a nonvolatile content of 50% by mass.

<Production of component (A-2)>
108.26 g polycarbonate diol (Asahi Kasei Chemicals, trade name “PCDL T-5651”), polycarbonate diol (Asahi Kasei Chemicals, trade name “PCDL T-5562”) 129.01 g, polybutadiene diol (manufactured by Nippon Soda Co., Ltd., (Product name “G-1000”) 70.49 g, 50.8 g of naphthalene diisocyanate, and 300 g of cyclohexanone were charged into a reaction vessel, heated to 80 ° C. to 90 ° C. with stirring under a nitrogen gas stream, and reacted for 9 hours. Subsequently, 5.10 g of 2-hydroxyethyl acrylate was added, and the reaction was performed until the absorption of isocyanate disappeared by infrared spectroscopic analysis to obtain a polyurethane acrylate resin having a number average molecular weight of 18,000. The obtained resin was diluted with cyclohexanone to obtain a polyurethane acrylate resin solution having a nonvolatile content of 50% by mass.

<Alternative (A) component: Preparation of component (A-3)>
Decamethylenebistrimellitic dianhydride (trade name “DBTA-KU”, manufactured by Kurokin Kasei Co., Ltd.) 7.3 g in a 300 mL four-necked separable flask equipped with a stirrer, thermometer, nitrogen inlet tube and phosphorus stack trap (0.014 mol), 18.05 g (0.056 mol) of benzophenonetetracarboxylic dianhydride (BTDA), [3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] 38.86 g (0.07 mol) of cyclohexene (manufactured by Cognis Japan, trade name “Versamine 551”) and 164 g of cyclohexanone were added, and the mixture was stirred at 40 ° C. for 15 minutes. After completion of the addition, the temperature was raised to 150 ° C., heated under reflux for 3 hours, and then dissolved. After desorption, the non-volatile content was adjusted to 30% by mass while stirring at 40 ° C. to obtain a cyclohexanone solution of a polyimide resin having a number average molecular weight of 25,000.

<Production of component (B-1)>
Polycarbonate diol (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name “PCDL T-6001” 100 g, m-xylylene diisocyanate 38.6 g, cyclohexanone 70.0 g were charged in a reaction vessel and stirred at 90 ° C. to 100 ° C. under a nitrogen gas stream. The reaction was carried out for 1 hour by heating to 0 ° C. Next, 23.8 g of 2-hydroxyethyl acrylate was added, and the reaction was carried out until the absorption of isocyanate disappeared by infrared spectroscopic analysis. (Non-volatile content 70 mass%) was obtained.

<Production of (B-2) Component>
Polycarbonate diol (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name “PCDL T-6001” 100 g, 1,5-naphthalene diisocyanate 43.2 g, cyclohexanone 72.0 g were charged in a reaction vessel and stirred under a nitrogen gas stream at 90 ° C. to The reaction was carried out for 1 hour by heating to 100 ° C. Next, 24.3 g of 2-hydroxyethyl acrylate was added, and the reaction was carried out until the absorption of isocyanate disappeared by infrared spectroscopic analysis. A solution (nonvolatile content: 70% by mass) was obtained.

<(B-3) component>
150 g of bisphenol F type epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name “YDF-8170C”), 67.8 g of acrylic acid, 0.07 g of methylhydroquinone, 1.5 g of triphenylphosphine and 145 g of cyclohexanone are charged into a reaction vessel and stirred. While heating to 100 ° C. to 105 ° C., the reaction was carried out for 20 hours to obtain an epoxy acrylate solution having a number average molecular weight of 500 (nonvolatile content 60% by mass).

<Preparation of curable resin composition>
Example 1
Dipentaerythritol hexaxane was added to 12.6 g (solid content: 6.3 g) of the above (A-1) polycarbonate-modified polyamideimide resin solution and 3.9 g (solid content: 2.7 g) of the above (B-1) polyurethane acrylate solution. 1.0 g of acrylate (trade name “Light acrylate DPE-6A” manufactured by Kyoeisha Chemical Co., Ltd.), 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one as component (C) (Ciba Specialty Chemicals, trade name “I-907”) and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Ciba Specialty Chemicals, product) 0.1 g of each of the names “I-369”), and polybutadiene modified epoxy resin (die) as component (D) 0.8 g of Le Chemical Co., Ltd., trade name “PB-3600”), and 0.8 g of microcapsule type thermal latent curing agent (trade name “Novacure HXA-3792”, manufactured by Asahi Kasei Chemicals Co., Ltd.) are added as component (E). Then, ethyl acetate was added so that the total solid content was 50% by mass, and the mixture was stirred at 40 ° C. for 1 hour to obtain a curable resin composition solution.

(Example 2)
(B) It replaced with (B-1) which is a component, and except having used (B-2), operation similar to Example 1 was performed and the curable resin composition solution was obtained.

(Example 3)
(B) It replaced with (B-1) which is a component, and except having used (B-3), operation similar to Example 1 was performed and the curable resin composition solution was obtained.

Example 4
(A) It replaced with (A-1) which is a component, and except having used (A-2), operation similar to Example 1 was performed and the curable resin composition solution was obtained.

(Comparative Example 1)
(E) Except not having added a component, operation similar to Example 1 was performed and the curable resin composition solution was obtained.

(Comparative Example 2)
(D) Except not adding a component, operation similar to Example 1 was performed and the curable resin composition solution was obtained.

(Comparative Example 3)
(A) It replaced with (A-1) which is a component, and performed the same operation as Example 1 except having used (A-3) which is an alternative (A) component, and set the curable resin composition solution. Obtained.

(Comparative Example 4)
A high heat-resistant insulating adhesive film (siloxane modified polyamideimide resin, manufactured by Hitachi Chemical Co., Ltd., trade name “KS-7003”) was prepared as a film adhesive.

  Table 1 summarizes the compounding ratios of the components of the curable resin composition solutions obtained in Examples 1 to 4 and Comparative Examples 1 to 3.

注）表中の値は、各成分の配合量（ｇ）を示す。また、表中の記号「−」は、該当する成分を含有していないことを示す。

Note) The values in the table indicate the blending amount (g) of each component. Further, the symbol “-” in the table indicates that the corresponding component is not contained.

(Preparation of peel strength test piece)
Examples 1 to 4 and Comparative Examples 1 to 3 were applied to a PET (polyethylene terephthalate) film so as to have a thickness of about 30 μm, dried at 100 ° C./15 minutes, cut into 10 cm length × 2 cm width, and curable. A PET film test piece with a resin composition was prepared.

The curable resin composition side of the obtained test piece is bonded to a silicon (Si) mirror wafer (thickness: 525 μm) with a urethane rubber roller on a hot plate heated to 80 ° C., and heated at 150 ° C./60 minutes. Two each were prepared (thermocompression bonding step). One of the produced test pieces was irradiated with ultraviolet rays (UV) at a dose of 1000 mJ / cm ² (wavelength 365 nm) from above the PET film.

  In Comparative Example 4, a PEN (polyethylene naphthalate) film was cut into a length of 10 cm × 2 cm and heated at 150 ° C. between the silicon mirror wafer (thickness of 525 μm) and the PEN film. In the state which pinched | interposed the 4 high heat-resistant insulation adhesive film, it adhere | attached with the urethane-type rubber roller, and heated 180 degreeC / 30 minutes additional (thermocompression bonding process).

(Evaluation of adhesion and peelability)
Using an autograph (manufactured by Shimadzu Corporation, trade name “AGS-H 100N”), the 180 ° peel strength of the test piece at room temperature was measured. The adhesion was evaluated by measuring the peel strength before UV irradiation. The peelability was evaluated by measuring the peel strength after UV irradiation. Furthermore, the presence or absence of deposits or residues on the silicon mirror wafer surface after the peelability evaluation (Si surface deposits after peeling) was observed visually. On the surface of the silicon mirror wafer, A having no deposits or residues derived from the curable resin composition was designated A, and B having deposits or residues derived from the curable resin composition was designated B.

注）表中の記載「＞２５」は、Ｓｉ基材が破壊したため、数値は最大値を示した。

Note) The description ">25" in the table shows the maximum value because the Si base material was destroyed.

Claims (6)

(A) a resin having a urethane bond,
(B) a photopolymerizable compound having an ethylenically unsaturated group,
(C) a photopolymerization initiator,
A curable resin composition comprising (D) an epoxy resin, and (E) an epoxy resin curing agent. The curable resin composition according to claim 1, wherein the resin (A) having a urethane bond is a resin having a structure represented by the following general formula (1).

[In Formula (1), R shows a C1-C18 alkylene group, X shows a bivalent organic group, and m and n show the integer of 1-30 each independently. A plurality of R may be the same or different. When n is 2 or more, a plurality of X and m may be the same or different. ]   The curable resin composition according to claim 1 or 2, wherein the resin (A) having a urethane bond is a resin having an amide bond and / or an imide bond.   The curable resin composition according to claim 1 or 2, wherein the resin (A) having a urethane bond is a resin having a polybutadiene skeleton and / or a polyisoprene skeleton.   The hardening as described in any one of Claims 1-4 in which the photopolymerizable compound which has the said (B) ethylenically unsaturated group contains the compound which has a 3 or more ethylenically unsaturated group in a molecule | numerator. Resin composition. The film adhesive formed by shape | molding the curable resin composition as described in any one of Claims 1-5 in a film form.