JPWO2016076209A1 - Two-component curable composition - Google Patents

Abstract

A compound having a (meth) acryl group, an acrylamide compound, water, an expandable capsule having a temperature of 70 to 95 ° C., a hydroperoxide, and a metal complex, and having a (meth) acryl group The two-part curable composition containing the expandable capsule in a proportion of more than 0 parts by mass and 50 parts by mass or less with respect to the part allows the cured product to be peeled from the adherend in a short time. In addition, it is possible to provide a curable composition in which contamination of the medium by the cured product after peeling is reduced. [Selection figure] None

Description

  The present invention relates to a two-component curable composition suitable for a temporary fixing agent.

  As a known technique related to a curable composition for temporary fixing such as an optical lens, a prism, an array, a silicon wafer, and a semiconductor mounting component, a two-component type temporary fixing agent as described in Patent Document 1 is known. Normally, a member that has been temporarily fixed by curing the curable composition is subjected to desired processing, and then the temporarily fixed cured material is peeled off in a heat medium (for example, hot water at 80 to 100 ° C.). And then subjected to the desired process. However, in the temporary fixing agent described in Patent Document 1, in the peeling test, the clearance between the adherends affecting the peeling speed is not mentioned, and further, the time for completing the peeling is 15 to 76 minutes. It takes time, and the peeling work takes a lot of time, and the workability is low. Furthermore, when a member having low heat resistance is used as the adherend, it is assumed that if the heat is continuously applied for a long time, the adherend is adversely affected.

JP 2007-039532 A

  Conventionally, when an adherend is bonded and temporarily fixed using a two-component curable composition, even if the clearance between the adherends is narrow, for example, in a medium (liquid) at 100 ° C. In less than 10 minutes, the adherend sometimes did not peel off. In addition, since the work of removing the cured product of the curable composition is usually performed in a medium (liquid, for example, water), it is necessary to frequently replace the medium when the cured product is collapsed. Incurs a decline. However, in the temporary fixing using the conventional two-component curable composition, the cured product after peeling often contaminates the medium, which hinders the work of the peeling process.

  Accordingly, an object of the present invention is to provide a curable composition in which a cured product of the curable composition can be peeled from an adherend in a short time, and contamination of the medium by the cured product after peeling is reduced. To do.

  As a result of intensive studies to achieve the above object, the present inventors have completed the present invention relating to a two-component curable composition suitable for temporary fixation.

The gist of the present invention will be described next. The first embodiment of the present invention is:
The following components (A) to (F) are included, and the first component and the second component include the following component (D) in a proportion of more than 0 parts by weight and 50 parts by weight or less with respect to 100 parts by weight of the following component (A): A two-component curable composition comprising two components;
(A) component: a compound having a (meth) acryl group,
(B) component: acrylamide compound,
(C) component: water,
(D) component: an expandable capsule having a temperature at which expansion starts to 70 to 95 ° C.,
(E) component: hydroperoxide, and (F) component: metal complex.

  Details of the present invention will be described below.

≪Curable composition≫
The first embodiment of the present invention includes the following components (A) to (F), and the following component (D) exceeds 50 parts by mass with respect to 100 parts by mass of the following (A) component. Is a two-component curable composition comprising a first liquid and a second liquid. Hereinafter, the “two-component curable composition” is also simply referred to as “curable composition”. In an embodiment, the curable composition is a two-part curable resin composition for temporary fixing.
(A) component: a compound having a (meth) acryl group,
(B) component: acrylamide compound,
(C) component: water,
(D) component: an expandable capsule having a temperature at which expansion starts to 70 to 95 ° C.,
(E) component: hydroperoxide, and (F) component: metal complex.

  ADVANTAGE OF THE INVENTION According to this invention, the hardened | cured material of a curable composition can be peeled from a to-be-adhered body in a short time, and contamination of the peeling work medium (liquid, for example, hot water) by the hardened | cured material after peeling was reduced. A curable composition can be provided. Although it does not restrict | limit the technical scope of this invention, it is estimated that this is based on the following mechanisms. That is, the curable composition concerning this invention contains (D) component. For this reason, (D) component expand | swells in the heat medium used for a peeling process, and the peelability of hardened | cured material expresses according to this. In addition, the curable composition according to the present invention combines the component (B) and the component (C) with the component (A) as a main component, although the detailed mechanism is unknown ( D) The peelability can be further improved as compared with the case of the component alone. From the above, the curable composition of the present invention has excellent releasability (becomes easy to peel after temporary fixing). Moreover, the excessive expansion | swelling of the hardened | cured material by (D) component is suppressed by making content of (D) component 50 mass parts or less with respect to 100 mass parts of (A) component, and it peeled from the to-be-adhered body. It can prevent that the hardened | cured material of a curable composition becomes brittle and micronized. Thereby, contamination of a peeling medium (for example, hot water) can be prevented and the peeling operation can be made efficient.

  However, the mechanism is speculation, and the technical scope of the present invention is not limited by the mechanism.

  Moreover, since the curable composition concerning this invention is a two-component curable composition containing a hydroperoxide and a metal complex, it can be cured at room temperature. Therefore, even when UV curing is difficult (for example, when an adherend has a shadow due to wiring or the like), there is an advantage that it can be easily cured.

  Embodiments of the present invention will be described below. In addition, this invention is not limited only to the following embodiment.

  In this specification, “X to Y” indicating a numerical range means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%. Further, in this specification, “(meth) acrylate” is used to mean both “acrylate” and “methacrylate”.

<(A) component: Compound having (meth) acrylic group>
The component (A) that can be used in the present invention is a compound having an acryl group and / or a methacryl group. Hereinafter, the acrylic group and the methacryl group are collectively referred to as a (meth) acryl group. In addition to imparting curability to the composition, the component (A) can also function as a solvent or dispersion medium for other components in the composition. The component (A) is suitable if the compatibility between the component (B) and the component (C) of the present invention is good. The component (A) can contain a (meth) acrylate oligomer component and / or a (meth) acrylate monomer.

  In the present invention, the “(meth) acrylate oligomer” is obtained by adding one or more (meth) acryl groups to an oligomer having a main skeleton such as epoxy resin, novolak, polybutadiene, polyester, polyether or the like. In this respect, the “(meth) acrylate oligomer” as the component (A) is a (meth) acrylic (co) polymer ((G) having a structural unit derived from a monomer having a (meth) acrylic group as a repeating unit. ) Component) is different. In the present specification, “oligomer” refers to a polymer having a weight average molecular weight of more than 500. In addition, the weight average molecular weight of a (meth) acrylate oligomer is a value measured by gel permeation chromatography (styrene conversion).

  Specific examples of the (meth) acrylate oligomer include (meth) acrylate oligomer having an ester bond in the molecule, (meth) acrylate oligomer having an ether bond, (meth) acrylate oligomer having a urethane bond, and epoxy-modified (meth) acrylate. Examples of the main skeleton include bisphenol A, novolak phenol, polybutadiene, polyester, and polyether, but are not limited thereto. Among the above, the (meth) acrylate oligomer component is preferably a (meth) acrylate oligomer (a polyester oligomer having a (meth) acryl group added) having an ester bond in the molecule.

  In addition, the component (A) that can be used in the present invention further includes a substituent other than the (meth) acrylic group, such as a compound having one or more epoxy groups and one or more acrylic groups in one molecule. Also included are compounds. Moreover, when (A) component contains the compound which has bifunctional or more (meth) acryl group, the hardened | cured material formed tends to become easy to peel. For this reason, when the cured product can be easily peeled off, the (meth) acrylate oligomer component contains an oligomer having a bifunctional or higher functional (meth) acryl group (a bifunctional or higher functional (meth) acrylate oligomer). preferable.

  As a (meth) acrylate oligomer having an ester bond, a synthesis in which an ester bond is formed by synthesis of a polyol and a polyvalent carboxylic acid and acrylic acid is added to an unreacted hydroxyl group is known. It is not limited to. Specifically, Aronix (registered trademark) M-6100, M-6200, M-6250, M-6500, M-7100, M-7300K, M-8030, M-8060, M- manufactured by Toa Gosei Co., Ltd. 8100, M-8530, M-8560, M-9050 and the like include, but are not limited to, UV-3500BA, UV-3520TL, UV-3200B, UV-3000B, etc. manufactured by Nippon Synthetic Chemical Industry Co., Ltd. It is not a thing.

  As a (meth) acrylate oligomer having an ether bond, a synthesis method in which acrylic acid is added to a hydroxyl group of a polyether polyol or a compound in which an alkylene oxide of a terminal hydroxyl group is added to an aromatic group such as bisphenol is known. However, it is not limited to this synthesis method. Specific examples include UV-6640B, UV-6100B, UV-3700B manufactured by Nippon Synthetic Chemical Industry, and Light Acrylate (registered trademark) 3EG-A, 4EG-A, 9EG-A, 14EG manufactured by Kyoeisha Chemical Co., Ltd. -A, PTMGA-250, BP-4EA, BP-4PA, BP-10EA, and the like, but are not limited thereto.

  As a (meth) acrylate oligomer having a urethane bond, a synthesis in which a urethane bond is formed by a polyol and a polyisocyanate and acrylic acid is added to an unreacted hydroxyl group is known. Specific examples include AH-600, AT-600, UA-306H, and UF-8001 manufactured by Kyoeisha Chemical Co., Ltd., but are not limited thereto.

  Known epoxy-modified (meth) acrylate oligomers include those obtained by adding (meth) acrylic acid to an epoxy group. As a specific example, Ebecryl (registered trademark) 3700 manufactured by Daicel Ornex Co., Ltd. is known, but is not limited thereto.

  As the component (A), a (meth) acrylate monomer can also be used. (A) component is 5-50 mass% of said (meth) acrylate oligomer with respect to the whole (A) component, and 95-50 mass% (meth) acrylate monomer (however, (meth) acrylate oligomer and ( The total amount with the (meth) acrylate monomer is 100% by weight.) Is preferable from the viewpoint of curability. More preferably, (A) component consists of 10-45 mass% of said (meth) acrylate oligomer, and 90-55 mass% of (meth) acrylate monomer.

  As the (meth) acrylate monomer, a monomer having one or more (meth) acryl groups in the molecule can be used. That is, monofunctional, difunctional, trifunctional and polyfunctional monomers can be used. Here, the (meth) acrylate monomer component includes a (meth) acrylate monomer having a hydroxyl group in the molecule, a (meth) acrylate monomer having an alicyclic hydrocarbon group in the molecule, and an ester bond in the molecule (meth). An acrylate monomer, a (meth) acrylate monomer having an ether bond, or the like can also be used. In particular, it is preferable to use a (meth) acrylate monomer having a hydroxyl group in the molecule because the compatibility between the (C) component water and the (A) component is improved. The proportion of the (meth) acrylate monomer having a hydroxyl group in the molecule is, for example, 5 to 50% by weight, preferably 10 to 40% by weight, based on the entire component (A).

  Specific examples of the monofunctional monomer include (meth) acrylic acid, lauryl (meth) acrylate, stearyl (meth) acrylate, ethyl carbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl ( (Meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate , Phenoxytetraethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, nonylphenoxytetraethylene glycol (meth) ) Acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, 2-ethylhexyl polyethylene glycol (meth) acrylate, nonylphenyl polypropylene glycol (meth) Acrylate, methoxydipropylene glycol (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (Meth) acrylate, epichlorohydrin (hereinafter abbreviated as ECH) (Meth) acrylate, ECH modified phenoxy (meth) acrylate, ethylene oxide (hereinafter abbreviated as EO) modified phthalic acid (meth) acrylate, EO modified succinic acid (meth) acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, morpholino (meth) acrylate, EO-modified phosphoric acid (meth) acrylate, and the like are exemplified, but the present invention is not limited to these. Absent.

  Specific examples of the bifunctional monomer include 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, 1,6-hexane glycol di (meth) acrylate, ethylene glycol diacrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, EO Modified neopentyl glycol di (meth) acrylate, propylene oxide side (hereinafter abbreviated as PO) modified neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, EO modified bisphenol A (Meth) acrylate, ECH-modified bisphenol A di (meth) acrylate, EO-modified bisphenol S di (meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol di (meta) ) Acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, EO modified dicyclopentenyl di (meth) acrylate, diacryloyl isocyanate Examples include, but are not limited to, nurate.

  Specific examples of the trifunctional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, ECH Examples thereof include, but are not limited to, modified trimethylolpropane tri (meth) acrylate, ECH-modified glycerol tri (meth) acrylate, and tris (acryloyloxyethyl) isocyanurate.

  Specific examples of the polyfunctional monomer include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipenta Examples include, but are not limited to, erythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

  As the component (A), from a group consisting of a compound having a molecular weight of 500 or less and having a hydroxyl group and a (meth) acryl group in the molecule and a compound having a molecular weight of 500 or less and a compound having an alicyclic group and a (meth) acryl group in the molecule. It is preferable to include at least one selected compound. From the viewpoint of improving the adhesive strength, it is more preferable that the component (A) includes a compound having a molecular weight of 500 or less and having a hydroxyl group and a (meth) acryl group in the molecule. At least one selected from the group consisting of a compound having a molecular weight of 500 or less and having a hydroxyl group and a (meth) acryl group in the molecule and a compound having a molecular weight of 500 or less and having an alicyclic group and a (meth) acryl group in the molecule. Among the compounds, specific examples of the monofunctional (meth) acrylate monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. However, it is not limited to these. At least one selected from the group consisting of a compound having a molecular weight of 500 or less and having a hydroxyl group and a (meth) acryl group in the molecule and a compound having a molecular weight of 500 or less and having an alicyclic group and a (meth) acryl group in the molecule. Among the compounds, specific examples of the bifunctional (meth) acrylate monomer include tricyclodecane dimethanol di (meth) acrylate.

  In this invention, said (A) component can be used individually by 1 type or in mixture of 2 or more types. Moreover, it is preferable that (A) component is liquid at 25 degreeC.

<(B) component: acrylamide compound>
The component (B) that can be used in the present invention is an acrylamide compound. By including the component (B), the compatibility between the component (A) and the component (C) is improved. Moreover, although it does not restrict | limit the technical scope of this invention, it is thought by containing (B) component that the water absorption of hardened | cured material improves and peelability improves by this.

  Specific examples of the component (B) include dimethyl (meth) acrylamide, (meth) acryloylmorpholine, diethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N- (2 -Methoxyethyl) (meth) acrylamide, diacetone (meth) acrylamide, N, N'-methylenebis (meth) acrylamide, and the like, but are not limited thereto. Considering the price and availability, diethyl (meth) acrylamide or dimethyl (meth) acrylamide is preferable. Although the cause has not been elucidated, the peelability of the cured product is further improved by combining the component (B) and the component (C) described later in the present invention. Specific examples of the component (B) include, but are not limited to, DMAA, ACMO, DEAA, and the like manufactured by KJ Chemical Co., Ltd.

  In this invention, said (B) component can be used individually by 1 type or in mixture of 2 or more types.

  It is preferable that 0.1-20 mass parts of (B) component is added with respect to 100 mass parts of (A) component. More preferably, (B) component is 0.1-10 mass parts with respect to 100 mass parts of (A) component. When the component (B) is 0.1 parts by mass or more, particularly more than 0.1 parts by mass, the peelability is better, and when the component (B) is less than 20 parts by mass, particularly less than 20 parts by mass, other components It becomes easy to make it compatible with. Furthermore, from the viewpoint of achieving both releasability and compatibility with other components, the component (B) is more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the component (A). preferable. In addition, when multiple types of compounds are included as (B) component, content of (B) component shall point out these total amounts.

<(C) component: water>
The component (C) that can be used in the present invention is water. By including the component (C), the peelability of the cured product is improved. The technical scope of the present invention is not limited, but this is presumed to be due to the following actions. That is, when a curable composition contains (C) component, a small amount of water will already exist in the hardened | cured material. Therefore, when the adherend is temporarily fixed and then the cured product is peeled in the medium, water is also present inside the cured product that is difficult for the medium to permeate.

  As the component (C), tap water, purified water using a purification device, ion exchange water, distilled water, and the like can be used. More preferably, the component (C) is purified water, ion exchange water or distilled water with less impurities. It is water.

  It is preferable that 0.1-20 mass parts of (C) component is added with respect to 100 mass parts of (A) component. More preferably, (C) component is 0.1-10 mass parts with respect to 100 mass parts of (A) component. When the component (C) is 0.1 parts by mass or more, particularly more than 0.1 parts by mass, good peelability can be maintained. (C) When a component is 20 mass parts or less, especially when it is less than 20 mass parts, it becomes compatible with another component easily. Furthermore, from the viewpoint of making the maintenance of peelability and compatibility with other components compatible, the component (C) is contained in an amount of 1 to 5 parts by mass with respect to 100 parts by mass of the component (A). And more preferred.

  Furthermore, the sum of the component (B) and the component (C) is preferably more than 0 parts by mass and 20 parts by mass or less with respect to 100 parts by mass of the component (A). More preferably, the sum of the component (B) and the component (C) is 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the component (A). Moreover, it is preferable that the said (B) component and said (C) component are contained with the same mass mutually from a viewpoint of peelability and adhesive strength.

<(D) component: expandable capsule whose temperature which starts expansion | swelling is 70-95 degreeC>
The component (D) that can be used in the present invention is an expandable capsule having a temperature at which expansion starts from 70 to 95 ° C. By including the component (D), the time required for peeling is shortened. In the case of an expandable capsule having an expansion start temperature of less than 70 ° C., the storage stability of the capsule is poor, so that the cured product tends to collapse in the peeling work medium (for example, hot water), and the medium is easily contaminated. There is. On the other hand, if the expandable capsule has a temperature at which expansion starts and exceeds 95 ° C., the peelability after temporary fixing is lowered.

  Preferably, the component (D) is an expandable capsule in which a hydrocarbon compound (core) that is liquid at 25 ° C. is encapsulated in an outer shell (shell) made of a thermoplastic resin such as polyvinylidene chloride resin or acrylic resin. More specifically, as the component (D), a liquid hydrocarbon compound (hydrocarbon compound that easily gasifies and expands by heating) at 25 ° C. is contained in the shell (the outer shell is made of an elastic outer shell material). It is preferable to use a thermally expandable fine spherical substance encapsulated in ().

  In the present specification, the temperature at which the component (D) starts to expand is measured by TMA (Thermo Mechanical Analysis), that is, by measuring the linear expansion coefficient. The initial volume under an atmosphere of 25 ° C. indicates a temperature at which the volume starts to expand due to the temperature rise.

  (D) A component can be used if the temperature which starts expansion | swelling (expansion start temperature) is partially contained in 70-95 degreeC. That is, the expansion start temperature of the following commercially available expandable capsules has a certain range, but at least a part of the temperature range from the lower limit value to the upper limit value of the expansion start temperature is 70 to 95 ° C. That's fine.

  (D) As a component, the thing whose temperature which starts expansion | swelling is 80-95 degreeC is more preferable.

  In particular, when the adherends are bonded together and temporarily fixed, it is easier to process if the cured product of the composition does not become thicker. For this reason, the average particle size (before expansion, diameter) of the component (D) is preferably small, specifically 100 μm or less, more preferably 70 μm or less, even more preferably less than 70 μm, and particularly preferably 50 μm or less. is there. The lower limit value of the average particle diameter of the component (D) is not particularly limited, but considering availability, it is preferably 1 μm or more, more preferably 10 μm or more, and particularly preferably more than 10 μm. In addition, said average particle diameter is a value of 50% average particle diameter in a laser particle size meter.

  Specific examples of the commercially available component (D) include Expandel (registered trademark) 031-40DU (expansion start temperature: 80 to 95 ° C.) manufactured by Nippon Philite Co., Ltd .; Matsumoto Microsphere (Matsumoto Yushi Seiyaku Co., Ltd.) (Registered trademark) F-30D (expansion start temperature: 70 to 80 ° C.), F-36D (expansion start temperature: 70 to 80 ° C.), F-36LVD (expansion start temperature: 75 to 85 ° C.); Examples thereof include, but are not limited to, Die Form (registered trademark) M-330 (expansion start temperature: 90 ° C.).

  In this invention, said (D) component can be used individually by 1 type or in mixture of 2 or more types.

  0.1-50 mass parts of (D) component is added with respect to 100 mass parts of (A) component in the curable composition which concerns on this invention. When the component (D) is added in an amount of 0.1 parts by mass or more, peelability is exhibited, and when the component (D) is 50 parts by mass or less, the expansion of the cured product after peeling is suppressed, which may hinder the peeling operation. It can be suppressed. Moreover, when (D) component exceeds 50 mass parts, the hardened | cured material of a curable composition expand | swells and becomes cotton-like, and a peeling medium is contaminated. From the viewpoint of releasability and prevention of contamination of the peeling work medium, the amount of the component (D) is preferably 5 to 50 parts by weight, more preferably 10 to 30 parts by weight with respect to 100 parts by weight of the component (A). Part. In addition, when several types of expansible capsule is included as (D) component, content of (D) component shall point out these total amounts.

<(E) component: hydroperoxide>
The component (E) that can be used in the present invention is hydroperoxide. Hydroperoxide is an organic peroxide having a structure of Formula 1. Here, R ¹ represents a chain aliphatic hydrocarbon, a cyclic aliphatic hydrocarbon, an aromatic hydrocarbon, or a derivative thereof. Specific examples include p-methane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and the like. It is not limited to.

  It is preferable that 0.01-5.0 mass parts of (E) component is added with respect to 100 mass parts of (A) component. (A) When the ratio of (E) component with respect to 100 mass parts of component is 0.01 mass part or more, especially more than 0.01 mass part, sclerosis | hardenability is easy to express when it contacts with (F) component, 5.0 When it is less than or equal to part by mass, particularly less than 5.0 parts by mass, the storage stability is good. The ratio of the component (E) to 100 parts by mass of the component (A) is more preferably 0.05 to 2.5 parts by mass. In addition, when several types of compounds are included as (E) component, content of (E) component shall point out these total amounts.

<(F) component: metal complex>
The component (F) that can be used in the present invention is a metal complex that decomposes the component (E). More specifically, the component (F) catalyzes a reaction that generates an alkoxy radical from hydroperoxide (component (E)).

  The component (F) that can be used in the present invention is particularly preferably a copper compound and / or a vanadium compound. A copper compound and / or a vanadium compound are preferable because high reactivity is obtained as compared with other metal compounds. Specific examples of the copper compound include, but are not limited to, copper chloride, copper acetate, copper naphthenate, copper acetylacetonate, and the like. Specific examples of the vanadium compound include, but are not limited to, vanadyl acetylacetonate, vanadium stearate, vanadium naphthate, vanadium pentoxide, and the like.

  (A) It is preferable that 0.01-1.0 mass part of (F) component is added with respect to 100 mass parts of component, The addition amount of (F) component more preferable is 0.01-0. 5 parts by mass. When the ratio of the component (F) to 100 parts by mass of the component (A) is 0.01 parts by mass or more, particularly more than 0.01 parts by mass, excellent curability when in contact with the component (E) is 1.0 parts by mass. Hereinafter, particularly when the amount is less than 1.0 part by mass, the storage stability is improved.

(Reaction accelerator)
Furthermore, an amine compound can be added to the curable composition for the purpose of improving the reaction between the component (E) and the component (F). Hereinafter, the component is referred to as a reaction accelerator or a curing accelerator. Specifically, tertiary amines such as saccharin, 1-acetyl-2-phenyl-hydrazine, N, N-dimethyl-p-toluidine, N, N-dimethylaniline, diisopropanol-P-toluidine, triethylamine, Examples include, but are not limited to, polyamines such as diethylenetriamine, triethylenetetramine, and pentaethylenehexamine, and thioureas such as thiourea, ethylenethiourea, benzoylthiourea, acetylthiourea, and tetramethylthiourea. . (A) It is preferable to add 0.01-5.0 mass parts of total reaction accelerators with respect to 100 mass parts of component. When the total amount is 0.01 parts by mass or more, particularly more than 0.01 parts by mass, the curability can be further improved, and when the total amount is 5.0 parts by mass or less, particularly less than 5.0 parts by mass, the storage stability is improved. Excellent in properties. The reaction accelerator (curing accelerator) may be one type or a combination of two or more types.

<(G) component: (meth) acrylic polymer>
Furthermore, in the present invention, a (meth) acrylic polymer that is liquid at 25 ° C. can be added as the component (G). That is, in one Embodiment of this invention, the curable composition which further contains a (meth) acrylic polymer liquid at 25 degreeC as (G) component is provided. In addition, the (meth) acrylic polymer as the (G) component refers to a (co) polymer having a structural unit derived from a monomer having a (meth) acrylic group as a repeating unit.

  The (meth) acrylic polymer may or may not contain a polar functional group or reactive functional group. Examples of the functional group having polarity include a hydroxyl group and a carboxyl group. Examples of the group include (meth) acryl group, epoxy group, hydrolyzable silyl group and the like, but are not limited thereto.

  By adding the (meth) acrylic polymer, the peelability is further improved. The viscosity at 25 ° C. is preferably 100 to 10000 mPa · s, more preferably 100 to 5000 mPa · s. If it is 100 mPa · s or more, bleeding out is difficult, and if it is 10000 mPa · s or less, compatibility with other components is good.

  Specific examples of commercially available products of component (G) include Alfon (registered trademark) UP-1000, UP-1020, UP-1021, UP-1061, UP-1110, UP-1110, etc. In addition to the registered trademark UP-1000 series, UH-2000 series, UC-3000 series, UG-4000 series, and the like may be mentioned, but the invention is not limited thereto.

  (A) With respect to 100 mass parts of component, (G) component is preferable in it being 0.1-30 mass parts, and it is more preferable that 0.1-20 mass parts is added. When the component (G) is 0.1 parts by mass or more, particularly more than 0.1 parts by mass, the releasability is improved, and when it is 30 parts by mass or less, particularly 20 parts by mass or less, the compatibility of the composition is improved (G ) Component bleed out is suppressed. The ratio of the component (G) to 100 parts by mass of the component (A) is more preferably 2 to 20 parts by mass.

  The weight average molecular weight of (G) component is 1,000-200,000, for example, Preferably it is 1,500-10,000.

<(H) component: Photoinitiator>
Furthermore, in this invention, you may add a photoinitiator in order to provide photocurability as (H) component. By adding a photoinitiator, the curing time can be shortened. That is, in one embodiment of the present invention, a curable composition further comprising a photoinitiator is provided.

  Specific examples of the component (H) include 1-hydroxycyclohexyl phenyl ketone, acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone. , 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 2,2-diethoxyacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 2,4,6-trimethylbenzophenone, oligo (2-hydroxy-2- Methyl-1- (4- (1-methylvinyl) phenyl) propanone), 4-allylacetophenone, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine Side, 4-methylbenzophenone, 4-chloro-4'-benzylbenzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8 -Nonylxanthone, benzoyl, benzoylmethyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, 2-chlorothioxanthone, o-methylbenzoate, benzyldimethyl ketal, methylbenzoylformate, etc. However, it is not limited to these. You may use these individually or in mixture of 2 or more types.

  It is preferable that 0.1-10 mass parts of photoinitiators are added with respect to 100 mass parts of (A) component. If it is 0.1 mass part or more, photocurability will be provided, and if it is less than 10 mass parts, especially less than 10 mass parts, it is excellent in storage stability. From the viewpoint of achieving both photocurability and storage stability, the component (H) is more preferably 0.2 to 4 parts by mass with respect to 100 parts by mass of the component (A). In addition, when multiple types of compounds are included as (H) component, content of (H) component shall point out these total amounts.

<(I) component:>
Furthermore, in the present invention, a thiol compound can be added as the component (I). Although the reason is not clearly clarified, in the present invention, by adding a thiol compound, it is possible to achieve both a prolonged pot life (pot life) and curability. That is, in one Embodiment of this invention, the curable composition which further contains a thiol compound as (I) component is provided. Examples of the thiol compound include compounds having 1 to 6 thiol groups in the molecule, such as linear, branched or cyclic alkanethiols having 1 to 18 carbon atoms; thioglycolic acid, mercaptopropionic acid, thiomalic acid Examples include mercaptocarboxylic acids such as ethylene glycol, polyethylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, hydroxyalkyl isocyanurate, and esters of the above mercaptocarboxylic acids. You may use these individually or in mixture of 2 or more types.

  Specific thiol compounds include dodecanethiol, tris-[(3-mercaptoproionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate) (PEMP), dipentaerythritol hexakis. (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, and the like, but are not limited thereto.

  Specific products that can be used as the component (I) include TEMPIC, PEMP, DPMP, TMMP manufactured by Sakai Chemical Industry Co., Ltd., TMTP, PETP, TMTG, PETG manufactured by Sakai Chemical Co., Ltd. It is not limited to these.

  It is preferable that 0.01-0.5 mass part of (I) component (thiol compound) is added with respect to 100 mass parts of (A) component. If the thiol compound is 0.01 parts by mass or more, particularly more than 0.01 parts by mass, the pot life after mixing the two liquids can be ensured, 0.5 parts by mass or less, especially less than 0.5 parts by mass. And the curability after mixing the two liquids becomes good. (A) With respect to 100 mass parts of component, (I) component is more preferable in it being 0.05-0.3 mass part. In addition, when several types of compounds are included as (I) component, content of (I) component shall point out these total amounts.

<Other ingredients>
An organic filler or an inorganic filler can be added to the curable resin according to the present invention. For the purpose of adjusting the viscosity, fumed silica can be added as an inorganic filler. Examples include, but are not limited to, hydrophilic types in which the surface is untreated and silanol remains, and hydrophobic types in which the silanol is treated with dimethyldichlorosilane to make the silica surface hydrophobic. . Specific examples of hydrophilic type products include Aerosil (registered trademark) 90, 130, 150, 200, 255, 300, and 380 manufactured by Nippon Aerosil Co., Ltd., and specific types of hydrophobic type products include Aerosil (registered trademark) R972 (dimethyldichlorosilane treatment), R974 (dimethyldichlorosilane addition), R104 (octamethylcyclotetrasiloxane treatment), R106 (octamethylcyclotetrasiloxane treatment), R202 (manufactured by Nippon Aerosil Co., Ltd.) Polydimethylsiloxane treatment), R805 (octylsilane treatment), R812 (hexamethyldisilazane treatment), R816 (hexadecylsilane treatment), R711 (methacrylsilane treatment) and the like. In addition, the Cabosil (registered trademark) series, which is fumed silica manufactured by Cabot Corporation, may be mentioned.

  Moreover, the said filler can also be added as a spacer. Particularly preferred are spherical resin beads. When a plate-shaped adherend is bonded and temporarily fixed, a substantially parallel resin layer is formed by adding spherical resin beads as a spacer to the temporary fixing agent. Specific examples of the raw material include (meth) acrylic resin and urethane resin resin beads, but are not limited thereto. The average particle size is preferably 1 to 100 μm, particularly preferably 10 to 70 μm. If it is 10 μm or more, particularly larger than 10 μm, it will be easy to peel off during the peeling operation. Specific examples of the spacer made of (meth) acrylic resin include Art Pearl (registered trademark) SE-050T manufactured by Negami Kogyo Co., Ltd., Gantz Pearl (registered trademark) GM-4003 manufactured by Ganz Kasei Co., Ltd. It is not limited to these.

  (A) It is preferable to add 0.1-30 mass parts of fillers with respect to 100 mass parts of component. When 0.1 part by mass or more of the filler is added, the fluidity after coating can be suppressed, and when 30 parts by mass or less is added, the storage stability is excellent.

  In addition, an antioxidant may be added to the curable resin according to the present invention depending on the purpose. Specifically, a phenol-based antioxidant, a thioether-based antioxidant, a phosphorus-based antioxidant, a nitroxide-based resin. Examples include, but are not limited to, antioxidants.

  In order to adjust the properties to the extent that the pot life of the present invention and the physical properties of the cured product are not impaired, various radical thermosetting agents, organic fillers, inorganic fillers, anti-aging agents, physical property adjusting agents, light stability You may mix | blend additives, such as an agent.

<Two-component curable composition>
Since the curable composition of the present invention is a two-component type, the curing reaction is unlikely to proceed during storage, and the storage stability is excellent compared to the one-component type. In the two-component curable composition, the content of each component is the amount of each component when the total amount of the component (A) contained in the first and second liquids is 100 parts by mass. is there. For example, the curable composition concerning this invention is (D) in 1st liquid and / or 2nd liquid with respect to 100 mass parts of total amounts of (A) component contained in 1st liquid and 2nd liquid. The total amount of components is more than 0 parts by mass and 50 parts by mass or less.

  In the two-component curable resin, the component (E) (hydroperoxide) is contained in one solution, the component (F) (metal complex) is contained in the other solution, By doing so, workability at the time of temporary fixing can be improved. That is, in one embodiment of the present invention, it comprises the first liquid and the second liquid, the component (A) is contained in the first liquid and the second liquid, and the component (B), the component (C) and the component (D). Is contained in the first liquid and / or the second liquid, the (E) component is contained in the first liquid, and the (F) component is contained in the second liquid. . From the viewpoint of better storage stability, the component (B) and the component (C) are included in the first solution containing the component (E), and the component (D) is included in the second solution containing the component (F). More preferably.

  The present invention is applied when the mixing ratio of the first liquid and the second liquid constituting the two-component curable composition (two-component temporary fixing composition) is 100: 70 to 130 (mass ratio). The first liquid and the second liquid are preferably adjusted so as to satisfy the composition of the curable composition. If it is in the said range, it can prevent that the hardening reaction which advances when measuring a liquid produces a bias, and can prevent that uncured partly generate | occur | produces. More preferably, when the mixing ratio of the first liquid and the second liquid is 100: 100 (mass ratio), the two-component curable composition is satisfied so as to satisfy the composition of the curable composition according to the present invention. Things are adjusted.

  When (I) component is contained in a composition, it is preferable to mix (F) component and (I) component just before use from a viewpoint of storage stability. That is, in one embodiment of the present invention, the component (A) is contained in the first liquid and the second liquid, and the components (B), (C), and (D) are the first liquid and / or the second liquid. The curable composition is provided in which the component (E) and the component (I) are contained in the first liquid, and the component (F) is contained in the second liquid.

  In the two-component curable composition according to the present invention, the component (A) which is liquid at room temperature (25 ° C.) is preferably used as a solvent or a dispersion medium. The ratio of the component (A) contained in the first liquid and the component (A) contained in the second liquid is not particularly limited, but is included in the first liquid and the second liquid from the viewpoint of workability for temporary fixing. (A) The mass ratio of a component becomes like this. Preferably it is 100: 70-130 (mass ratio), More preferably, it is 100: 90-110 (mass ratio), More preferably, it is 100: 100 (mass ratio). .

  In preferable one Embodiment of this invention, a curable composition is (A) component 100 mass parts (total amount of (A) component contained in 1st liquid, and (A) contained in 2nd liquid). On the other hand, 0.1-20 mass parts of (B) component, 0.1-20 mass parts of (C) component, 0.01-5.0 mass parts of (E) component, and (F) component. It is included at a ratio of 0.01 to 1.0 part by mass.

<Temporary fixative>
As another embodiment, the present invention also provides a temporary fixative containing the two-component curable composition. Since the temporary fixing agent according to the present invention contains the curable composition, it temporarily fixes even when it is used with a narrow clearance when temporarily fixing a large-area plate-shaped adherend by adhesion. It is particularly suitable and can be easily peeled off after processing the adherend.

(Method of temporarily fixing the adherend)
After coating the curable composition or temporary fixing agent of the present invention on the adherend, it is placed on the object (other adherend) to fix the adherend (one adherend) and pressed. When the component (H) is contained, the curable composition (or temporary fixing agent) is cured by further irradiating with light if desired. The curable composition or temporary fixing agent of the present invention may be applied to one of the adherend and the other adherend, or may be applied to both.

  As a curing method, the first liquid is applied to one adherend, the second liquid is applied to the other adherend, the first liquid and the second liquid are brought into contact with each other, and two adherends are applied. A method of temporarily fixing the adherend by bonding the adherends, or mixing the first liquid and the second liquid, and applying the mixed liquid to one or both adherends, There is a method of temporarily fixing the adherend by bonding the adherend, but the method is not limited thereto. That is, the second liquid is applied to an adherend different from the adherend to which the first liquid is applied, and the first liquid coating film and the second liquid coating film are brought into contact with each other. May be adhered. Or after mixing a 1st liquid and a 2nd liquid, the coating film of the obtained mixture may be formed on a to-be-adhered body, and a to-be-adhered body may be adhere | attached through the said coating film. The adherend is temporarily fixed to the fixed object by the cured product derived from the curable composition. In one embodiment of the present invention, a method of temporarily fixing an adherend using the two-component curable composition described above, wherein the first liquid coating film formed on one adherend and the other There is provided a method of temporarily fixing an adherend, which comprises bringing the second liquid coating film formed on the adherend into contact. In another embodiment of the present invention, a method of temporarily fixing an adherend using the above two-component curable composition, wherein a mixture of the first liquid and the second liquid is prepared, There is provided a method of temporarily fixing the one adherend and the other adherend through a coating film of the mixture formed on at least one surface of the adherend and the other adherend. .

The pressure when pressing the adherend is not particularly limited, and is appropriately determined according to the material of the adherend. Further, the light irradiation conditions when the component (H) is used are not particularly limited. For example, the irradiation energy amount (integrated light amount) of ultraviolet light can be 10 to 10,000 mJ / cm ² , preferably The irradiation energy amount (integrated light amount) of ultraviolet light is 100 to 5000 mJ / cm ² .

  The two-component curable composition of the present invention exhibits releasability from an adherend in a medium. Therefore, as still another embodiment of the present invention, the cured product obtained by curing the curable composition or the temporary fixing agent is immersed in a medium of 90 ° C. or higher (for example, 90 to 110 ° C.) to cure the cured product. There is also provided a method for temporarily fixing an adherend comprising peeling an object from the adherend.

  Examples of the peeling medium include hot water at 90 to 100 ° C. and medium at 90 to 200 ° C. As the medium at 100 to 200 ° C., a mixture of water and a water-soluble organic solvent having a boiling point of 100 ° C. or higher can be used. As the water-soluble organic solvent, ethylene glycol, propylene glycol or the like can be used alone or in combination, and can be arbitrarily mixed as long as a specific temperature can be set. In order to sufficiently fix the adherend temporarily and to peel the cured product without remaining on the adherend, it is necessary to peel in a medium of 90 to 200 ° C. The resin composition concerning this invention can peel hardened | cured material in a 90 degreeC or more medium. In particular, the present invention, which can be peeled off in a medium at 90 ° C. to 200 ° C., is excellent in the ability to temporarily fix the adherend, and can be temporarily fixed without being peeled against stress applied from the outside during processing operations. it can. Preferably, the peel time of the cured product is less than 10 minutes in hot water at 100 ° C., more preferably within 7.5 minutes, and even more preferably within 5 minutes. Specifically, the evaluation method of the peeling time of the cured product in hot water at 100 ° C. is measured by the method of “Peelability confirmation” described in the examples. The two-component curable composition of the present invention is suitable for applications in which an adherend is temporarily fixed to perform work steps such as cutting and polishing. Examples of the adherend include, but are not limited to, a silicon wafer, sapphire glass, ceramic material, optical glass, crystal, and magnetic material.

<Embodiment>
Although preferable embodiment of this invention is shown below, this invention is not limited to the following forms.
(1-1) The following (A) to (F) components are included, and with respect to 100 parts by mass of the following (A) component, the following (D) component is included in a proportion of more than 0 part by mass and 50 parts by mass or less. A two-pack curable composition comprising a first liquid and a second liquid;
(A) component: a compound having a (meth) acryl group,
(B) component: acrylamide compound,
(C) component: water,
(D) component: an expandable capsule having a temperature at which expansion starts to 70 to 95 ° C.,
(E) component: hydroperoxide, and (F) component: metal complex.
(1-2) The two-component curable composition according to (1-1), which includes a compound having a molecular weight of 500 or less and a hydroxyl group and a (meth) acryl group in the molecule as the component (A).
(1-3) The curable composition according to (1-1) or (1-2), further including a (meth) acrylic polymer that is liquid at 25 ° C. as the component (G).
(1-4) The curable composition according to any one of (1-1) to (1-3), further including a photoinitiator as the component (H).
(1-5) The curable composition according to any one of (1-1) to (1-4), further including a thiol compound as the component (I).
(1-6) The component (A) is contained in the first liquid and the second liquid, and the component (B), the component (C), and the component (D) are the first liquid and / or the Any of (1-1) to (1-5), which is contained in the second liquid, the (E) component is contained in the first liquid, and the (F) component is contained in the second liquid. The two-component curable composition according to one.
(1-7) The component (B) and the component (C) are included in the first liquid, and the component (D) is included in the second liquid. (1-1) to (1-6) The two-component curable composition according to any one of the above.
(1-8) 0.1-20 parts by mass of (B) component, 0.1-20 parts by mass of (C) component, and (E) component with respect to 100 parts by mass of (A) component 0.01 to 5.0 parts by mass, and the component (F) is contained in a ratio of 0.01 to 1.0 part by mass, and any one of (1-1) to (1-7) Two-component curable composition.
(1-9) The curable composition according to any one of (1-1) to (1-8), which can peel a cured product in a medium at 90 ° C. or higher.
(1-10) The two-component curable composition according to any one of (1-1) to (1-9), wherein a peel time of the cured product is less than 10 minutes in 100 ° C. hot water. object.
(1-11) A method of temporarily fixing an adherend using the two-component curable composition according to any one of (1-1) to (1-10),
Preparing a mixture of the first liquid and the second liquid;
A method of temporarily fixing the one adherend and the other adherend through a coating film of the mixture formed on at least one surface of the one adherend and the other adherend.
(1-12) A method of temporarily fixing an adherend using the two-component curable composition according to any one of (1-1) to (1-10),
Preparing a mixture of the first liquid and the second liquid;
A method of temporarily fixing the one adherend and the other adherend through a coating film of the mixture formed on at least one surface of the one adherend and the other adherend.
(1-13) A temporary fixing agent comprising the two-component curable composition according to any one of (1-1) to (1-10).
(2-1) A two-component curable composition comprising the components (A) to (E), wherein 50 parts by mass or less of the component (D) is added to 100 parts by mass of the component (A);
(A) component: a compound having a (meth) acryl group,
(B) component: acrylamide compound,
(C) component: water,
(D) component: an expandable capsule having a temperature at which expansion starts to 70 to 95 ° C.,
(E) component: hydroperoxide, and (F) component: metal complex.
(2-2) The component (A) has a molecular weight of 500 or less and a compound having a hydroxyl group and a (meth) acryl group in the molecule and a molecular weight of 500 or less and an alicyclic group and a (meth) acryl group in the molecule. The two-component curable composition according to (2-1), comprising at least one compound selected from the group consisting of compounds.
(2-3) The two-component curable composition according to (2-1) or (2-2), further comprising a (meth) acrylic polymer that is liquid at 25 ° C.
(2-4) The two-component curable composition according to any one of (2-1) to (2-3), further including a photoinitiator.
(2-5) The two-component curable composition according to any one of (2-1) to (2-4), further including a thiol compound.
(2-6) The first composition contains the component (A), the component (B), the component (C) and the component (E), and the second composition contains the component (A), the component (D) and the component (F). The two-component curable composition according to any one of (2-1) to (2-5), comprising a component.
(2-7) The two-component curable composition according to any one of (2-1) to (2-6), which can peel a cured product in a medium at 90 ° C or higher.
(2-8) A temporary fixing agent comprising the two-component curable composition according to any one of (2-1) to (2-7).
(2-9) With the two-component curable composition according to any one of (2-1) to (2-7), the first composition is applied to one adherend, and the other A method of temporarily fixing an adherend by applying a second composition to the adherend, bringing the first composition and the second composition into contact, and bonding the two adherends together.
(2-10) After mixing the first composition and the second composition of the two-component curable composition according to any one of (2-1) to (2-7), one or both A method of temporarily fixing an adherend by applying the mixed composition to the adherend and bonding the two adherends together.

  EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited only to these Examples.

[Examples 1-7, Comparative Examples 1-7]
In order to prepare a two-pack curable composition, the following components were prepared. (Hereinafter, the first and second liquids of the two-component curable composition are referred to as “agent A” and “agent B”, respectively, and the mixture of agent “A” and agent B is simply referred to as “mixture”).
((A) component: a compound having a (meth) acrylic group)
・ Polyfunctional polyester acrylate (Aronix (registered trademark) M-8060 manufactured by Toagosei Co., Ltd.)
-Bifunctional polyester acrylate (Aronix (registered trademark) M-6200, manufactured by Toagosei Co., Ltd.)
Polyethylene glycol diacrylate (Light acrylate (registered trademark) 14EG-A manufactured by Kyoeisha Chemical Co., Ltd.)
Tricyclodecane dimethanol diacrylate (Light acrylate (registered trademark) DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.): a compound having a molecular weight of 500 or less and an alicyclic group and an acrylic group (acryloyl group) in the molecule. Ethyl carbitol acrylate (Biscoat # 190 Osaka Organic Chemical Industry Co., Ltd.)
2-hydroxyethyl methacrylate (manufactured by Nippon Shokubai Co., Ltd.): a compound having a molecular weight of 500 or less and a hydroxyl group and a methacryl group (methacryloyl group) in the molecule (component (B): acrylamide compound)
・ Dimethylacrylamide (manufactured by DMAA KJ Chemical Co., Ltd.)
((C) component: water)
・ Purified water (manufactured by Kyoei Pharmaceutical Co., Ltd.)
((D) component: expandable capsule having a temperature of 70 to 95 ° C. for starting expansion)
Expandable capsule having an expansion start temperature of 80 to 95 ° C. (average particle diameter (diameter): 13 μm) (Expancel (registered trademark) 031-40DU manufactured by Nippon Philite Co., Ltd.)
((D ′) component: expandable capsules other than (D) component)
Expandable capsule having an expansion start temperature of 108 to 113 ° C. (average particle diameter (diameter): 12 μm) (Expancel (registered trademark) 051-40DU manufactured by Nippon Philite Co., Ltd.)
((E) component: hydroperoxide)
Cumene hydroperoxide (Park Mill (registered trademark) H-80 manufactured by NOF Corporation)
((F) component: metal complex)
-Copper naphthenate (Naftex copper (Cu 5%) manufactured by Nippon Chemical Industry Co., Ltd .: CAS No. 1338-02-9)
((G) component: (meth) acrylic polymer which is liquid at 25 ° C.)
A (meth) acrylic polymer having no functional group with a viscosity of 1000 mPa · s (25 ° C.) (Alfon (registered trademark) UP-1000, manufactured by Toagosei Co., Ltd., Mw: 3000)
((H) component: photoinitiator)
1-hydroxycyclohexyl phenyl ketone (manufactured by Suncure84 Chemical Chemical Co., Ltd.)
((I) component: thiol compound)
Pentaerythritol tetrakis (3-mercaptopropionate) (PEMP, manufactured by Sakai Chemical Industry Co., Ltd.)
(Reaction accelerator)
・ Saccharin (reagent)
1-acetyl-2-phenyl-hydrazine (reagent)
・ N, N-dimethyl-p-toluidine (reagent)
(filler)
-Dimethyldichlorosilane-modified amorphous silica (average particle diameter (diameter): 16 nm) (Aerosil (registered trademark) R972, manufactured by Nippon Aerosil Co., Ltd.)
Acrylic beads (average particle diameter (diameter): 40 μm) (Ganz Pearl (registered trademark) GM-4003 manufactured by Ganz Kasei Co., Ltd.).

  Agent A was prepared as follows. That is, among the components constituting the agent A shown in Table 1, (D) component (or (D ′) component), (E) component, (H) component, each component excluding reaction accelerator and filler Was weighed in a stirring kettle and stirred for 30 minutes to be uniform. Thereafter, the component (E), the component (H), and optionally the reaction accelerator were weighed in a stirring vessel and stirred for 30 minutes while defoaming. Finally, the component (D) (or the component (D ′)) and the filler were weighed in a stirring vessel and further prepared by stirring for 15 minutes while degassing.

  Agent B was prepared as follows. That is, among the components constituting the B agent shown in Table 1, (D) component (or (D ′) component), (F) component, (H) component, each component excluding reaction accelerator and filler Was weighed in a stirring kettle and stirred for 30 minutes to be uniform. Thereafter, the component (F), the component (H), and optionally the reaction accelerator were weighed in a stirring vessel and stirred for 30 minutes while degassing. Finally, the component (D) (or the component (D ′)) and the filler were weighed in a stirring vessel and further prepared by stirring for 15 minutes while degassing.

  Detailed preparation amounts of the A agent and B agent are in accordance with Table 1, and all numerical values are expressed in parts by mass. In addition, Table 2 summarizes the preparation amounts of the mixture obtained by weighing A agent and B agent in a mass ratio of 1: 1 and stirring uniformly. All numerical values in Table 2 are expressed in parts by mass.

[Viscosity measurement]
Immediately after production (within about 1 hour), “viscosity (mPa · s)” was measured when the viscosities of agent A and agent B were measured with an E-type viscometer at 25 ° C. and 20 rpm for 3 minutes. The viscosity is preferably 500 mPa · s or less. When the viscosity is 500 mPa · s or less, there is little stringing at the time of coating, and leveling properties are good.

[Confirm storage stability]
The viscosity after preparation of the A agent and the B agent was measured by the same method as the above viscosity measurement, and was set as “initial viscosity (mPa · s)”. Agent A and Agent B were allowed to stand in an atmosphere of 25 ° C. for 30 days, and then the viscosity was measured again to obtain “viscosity after standing (mPa · s)”. “Change rate (%)” = (viscosity after standing−initial viscosity) / initial viscosity × 100, and evaluated according to the following evaluation criteria to obtain storage stability. The rate of change is preferably “◯” or “Δ”, and more preferably “◯”.
<Evaluation criteria>
○: Change rate is 20% or less Δ: Change rate is greater than 20% and 50% or less ×: Change rate is greater than 50%

  From the comparison between Examples 4 and 5, the curable composition was a first liquid containing (A) component, (B) component, (C) component and (E) component, (A) component, and (D) component. And it turns out that storage stability improves by setting it as the 2 liquid type which consists of a 2nd liquid containing (F) component. From the viewpoint of storage stability, it is more preferable to store the component (F) and the component (I) as separate solutions from the comparison between Examples 1 to 4 and Example 5.

  About Examples 1-7 and Comparative Examples 1-7, tensile shear adhesive strength measurement, peelability confirmation, and cured product state confirmation after peeling were measured and confirmed, and are summarized in Table 3.

  [Measurement of tensile shear bond strength] Agent A and Agent B are weighed in a container so as to have a ratio of 1: 1 (w / w), and mixed at 150 rpm for 30 seconds using a defoaming agitator combined with rotation and revolution. After that, it was applied to the adherend by the following procedure within 5 minutes.

  For the tensile shear bond strength, two glass plates each having a thickness of 5 mm, a width of 25 mm, and a length of 100 mm were used as adherends. That is, a mixture of agent A (first liquid) and agent B (second liquid) was applied to one glass plate. Then, the other glass plate was quickly bonded together and fixed with a jig so that the adhesion surface was 25 mm × 10 mm. The glass plate bonded through the mixture was allowed to stand for 1 day (24 hours) in an atmosphere at 25 ° C. to prepare a test piece having a thickness (clearance) of the adhesive layer (cured product) of 60 μm. Measurement was performed by using a test piece and pulling in a shearing direction at a speed of 50 mm / min with a tensile tester. “Maximum strength (N)” was measured and calculated from the adhesion area to be “adhesion strength (MPa)”. When the glass plate was peeled off before measurement (for example, when handling a test piece), it was described as “NG”. From the viewpoint of preventing the adherend from falling off during processing operations in actual use, the adhesive strength is preferably 1 MPa or more, more preferably 2 MPa or more, and even more preferably 2.6 MPa or more.

[Peelability check]
Mixture of agent A (first solution) and agent B (second solution) on a glass plate of length 100 mm × width 100 mm × thickness 0.7 mm (agent A: agent B = 1: 1 (w / w) ) Painted. Another glass plate having the same shape was bonded to the glass plate coated with the mixture, and pressure was applied until the mixture (curable composition) was uniform on the glass surface. Thereafter, the composition was cured by UV irradiation at 3000 mJ / cm ² to prepare a test piece. The thickness (clearance) of the cured product of the test piece was 60 μm. The test piece was immersed in hot water at 100 ° C., and the time when the cured product was peeled from the glass plate was defined as “peelability (min)”. In Table 3, when it did not peel in 60 minutes, it described as "NG", and described as "-", without performing another test and measurement. The “peelability (min)” is preferably less than 10 minutes.

[Confirmation of cured product state after peeling]
The state of the cured product peeled from the glass plate by the above “peelability confirmation” was visually confirmed and judged according to the following evaluation criteria. The judgment result is shown in Table 3 as “cured product state after peeling”. When the peeled cured product expands, the work is bulky and troubles are generated. Therefore, it is preferable that the cured product is peeled as it is without expanding. When peelability was NG, the cured product state after peeling was described as “−”.
<Evaluation criteria>
◯: The cured product was peeled off without swelling. ×: The cured product was swollen to become cotton-like and peeled off.

  When Examples 1 to 7 and Comparative Examples 1 to 4 are compared, the composition containing (D) component that does not contain (B) component and (C) component as in Comparative Examples 1 to 4 has sufficient peelability. It did not develop and took 10 minutes or more to peel from the adherend. Further, when Examples 1 to 7 and Comparative Example 5 are compared, the composition containing (B) and (C) components that do not contain the component (D) as in Comparative Example 5 does not exhibit the peelability. It was. Furthermore, from the comparison between Comparative Example 4 and Comparative Example 6, as in Comparative Example 6, in the composition containing more than 50 parts by mass of component (D) with respect to 100 parts by mass of component (A), the cured product peeled off Swelled and contaminated the media. In Comparative Example 7, since the component (D) was not used, the peelability was not exhibited.

  In addition, this application is based on the JP Patent application No. 2014-229461 for which it applied on November 12, 2014, The content of an indication is referred to this indication as a whole by reference.

  The two-component curable composition of the present invention can be easily peeled in a medium at 90 to 200 ° C., even though the adherend is surface-bonded. The adherend can be used for various materials such as a silicon wafer, sapphire glass, ceramic material, optical glass, crystal, and magnetic material, and can be used for a general purpose in a temporary fixing process.

Claims (13)

The following components (A) to (F) are included, and the first component and the second component include the following component (D) in a proportion of more than 0 parts by weight and 50 parts by weight or less with respect to 100 parts by weight of the following component (A): A two-component curable composition comprising two components;
(A) component: a compound having a (meth) acryl group,
(B) component: acrylamide compound,
(C) component: water,
(D) component: an expandable capsule having a temperature at which expansion starts to 70 to 95 ° C.,
(E) component: hydroperoxide, and (F) component: metal complex.   The two-component curable composition according to claim 1, comprising a compound having a molecular weight of 500 or less and having a hydroxyl group and a (meth) acryl group in the molecule as the component (A).   The two-component curable composition according to claim 1 or 2, further comprising a (meth) acrylic polymer that is liquid at 25 ° C as the component (G).   The two-component curable composition according to any one of claims 1 to 3, further comprising a photoinitiator as the component (H).   The two-component curable composition according to any one of claims 1 to 4, further comprising a thiol compound as the component (I). The component (A) is contained in the first liquid and the second liquid,
The component (B), the component (C) and the component (D) are contained in the first liquid and / or the second liquid,
The two-component curable composition according to any one of claims 1 to 5, wherein the component (E) is contained in the first liquid, and the component (F) is contained in the second liquid.   The two-component type according to any one of claims 1 to 6, wherein the component (B) and the component (C) are contained in the first liquid, and the component (D) is contained in the second liquid. Curable composition.   The component (B) is 0.1 to 20 parts by mass, the component (C) is 0.1 to 20 parts by mass, and the component (E) is 0.01 to 100 parts by mass of the component (A). The two-component curable composition according to any one of claims 1 to 7, comprising 5.0 parts by mass and the component (F) at a ratio of 0.01 to 1.0 part by mass.   The two-component curable composition according to any one of claims 1 to 8, wherein the cured product can be peeled in a medium at 90 ° C or higher.   The two-component curable composition according to any one of claims 1 to 9, wherein the peel time of the cured product is less than 10 minutes in hot water at 100 ° C. A method of temporarily fixing an adherend using the two-component curable composition according to any one of claims 1 to 10,
A method for temporarily fixing an adherend, comprising bringing a coating film of the first liquid formed on one adherend into contact with a coating film of the second liquid formed on another adherend. A method of temporarily fixing an adherend using the two-component curable composition according to any one of claims 1 to 10,
Preparing a mixture of the first liquid and the second liquid;
A method of temporarily fixing the one adherend and the other adherend through a coating film of the mixture formed on at least one surface of the one adherend and the other adherend.   The temporary fixative containing the two-component curable composition of any one of Claims 1-10.