JP2013071984A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated substrate having high coating properties, high transparency, flatness, and processability.SOLUTION: In the laminated substrate, a curable resin composition layer is formed when a composition having a solution viscosity of ≤5 Pas at 23°C and including following components (A) to (D) as essential components is put between a first substrate with a thickness of <1 mm and a second substrate with a thickness of <1 mm, and then subjected to photoirradiation and heating at ≥80°C to be cured. In the curable resin composition layer, a tensile storage modulus at 23°C is ≥1,700 MPa, and that at 100°C is ≤70 MPa. The component (A) is a compound having at least two carbon-carbon double bonds in one molecule. The component (B) is a compound including linear and/or cyclic polysiloxane skeleton and having at least one SiH group and at least one epoxy group and/or oxetanyl group in one molecule. The component (C) is a cationic photopolymerization initiator. The component (D) is a thermal hydrosilylation catalyst.

Description

  The present invention relates to a bonded substrate having high coatability and transparency, flatness and workability.

  In an optical semiconductor device such as a CMOS image sensor, as a semiconductor element is miniaturized and highly integrated, a substrate on which a semiconductor element is formed, for example, a silicon substrate is thinned and bonded to another substrate for processing. Is adopted. For example, a silicon semiconductor substrate having a surface formed with an optical semiconductor device such as a CMOS is bonded to a glass substrate through a bonding sealing material. These optical semiconductor devices can be produced at the wafer level, and the bonded substrates are separated and mounted on a printed board or the like.

  Here, as a sealing material used for bonding, high transparency for use as a device and flat sealing without warping are required. Furthermore, high workability such as dicing performed after sealing at wafer level is required.

  Patent Document 1 describes a photosensitive resin composition containing organosiloxane as a CMOS image sensor sealing material. However, the photosensitive resin composition described in Patent Document 1 has insufficient transparency, the hardness of the cured sealing material is low, and there is room for improvement in workability.

JP2009-270027A

  An object of the present invention is to provide a bonded substrate having high coatability and transparency, flatness and workability.

In view of the above circumstances, as a result of extensive studies by the present inventors, the present invention has the following configuration.
That is, the present invention has the following configuration.

1). The composition having the following components (A) to (D) as essential components, having a solution viscosity at 23 ° C. of 5 Pa · s or less, includes a first substrate having a thickness of less than 1 mm and a second substrate having a thickness of less than 1 mm. A curable resin composition layer cured by light irradiation and application of heat of 80 ° C. or more after being sandwiched between them is formed, and the tensile storage elasticity of the curable resin composition layer at 23 ° C. A bonded substrate having a modulus of 1700 MPa or more and a tensile storage modulus at 100 ° C. of 70 MPa or less.
(A) A compound having at least two carbon-carbon double bonds in one molecule (B) containing a chain and / or cyclic polysiloxane skeleton, at least one SiH group in one molecule, and an epoxy group And / or a compound having at least one oxetanyl group (C) photocationic polymerization initiator (D) thermal hydrosilylation catalyst 2). (A) The bonded substrate as described in 1) above, wherein the component has a molecular weight of 2000 or less.

  3). Furthermore, the compound board | substrate as described in any one of 1) -2) characterized by including the compound which has one carbon-carbon double bond in 1 molecule as (E) component.

  4). The carbon-carbon double bond contained in the composition is 1.0 to 2.7 mmol / g, the epoxy group and / or the oxetanyl group is 1.0 to 2.4 mmol / g, and is derived from the component (E) The bonded substrate according to 3), wherein the amount of carbon-carbon double bonds is in the range of 0.01 to 1.8 mmol / g.

  5). The bonded substrate according to any one of 1) to 4), wherein an isocyanuric acid ring structure is contained in the composition.

6). (B) The bonded substrate according to any one of 1) to 5), wherein the component uses a hydrosilylation reaction product of the following compounds (α) to (γ).
(Α) Organic compound having one or more carbon-carbon double bonds having reactivity with SiH group in one molecule (β) Organosiloxane compound (γ) 1 having at least three SiH groups in one molecule Compound having in its molecule at least one epoxy group and / or oxetanyl group and one or more carbon-carbon double bond having reactivity with SiH group 7). (B) At least one of the epoxy group and / or oxetanyl group contained in the component is an alicyclic epoxy group, an oxetanyl group, or a glycidyl group, according to any one of 1) to 6) Bonded substrate.

  8). (C) Component is an onium salt, The bonded substrate as described in any one of 1) -7) characterized by the above-mentioned.

  9). Furthermore, a sensitizer is contained as (F) component, The bonded substrate as described in any one of 1) -8) characterized by the above-mentioned.

  10). The bonded substrate according to any one of 1) to 9), wherein the substrate is selected from a silicon substrate and / or a glass substrate.

  11). A semiconductor product incorporating a component obtained by dicing the bonded substrate according to any one of 1) to 10).

  According to the present invention, a bonded substrate having high applicability and transparency, flatness, and workability can be provided.

Hereinafter, the present invention will be described in detail.
((A) component)
The component (A) is not particularly limited as long as it is a compound having at least two carbon-carbon double bonds in one molecule. (A) The compound contained in a component may be single or multiple.
Although it does not restrict | limit especially as a carbon-carbon double bond contained in (A) component, The carbon-carbon double bond shown by the following general formula (I) is preferable from a reactive point.

(In the formula, R ¹ represents a hydrogen atom or a methyl group.) From the standpoint of availability of raw materials, R ¹ is more preferably a hydrogen atom.
General formula (II) is preferable from the point that the heat resistance of hardened | cured material is high.

(In the formula, R ² represents a hydrogen atom or a methyl group, and each R ² may be the same or different.) In view of the availability of raw materials, R ² is more preferably a hydrogen atom. .

  The carbon-carbon double bond may be covalently bonded to the skeleton of the component (A) via a substituent, and the substituent is selected from C, H, N, O, S and halogen as constituent elements. Those containing only atoms are preferred. The following are mentioned as an example of a substituent.

  Two or more of these substituents may be connected by a covalent bond to form a substituent.

  Examples of the group covalently bonded to the skeleton as described above include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3 -Allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyl) Examples include oxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group, and those shown below.

  From the viewpoint of further improving the heat resistance, the carbon-carbon double bond contained per gram of component (A) is preferably 1 mmol or more, more preferably 2 mmol or more, and 3 mmol or more. Is particularly preferred.

  The component (A) preferably has a molecular weight of less than 2000, preferably less than 1500 from the viewpoint of high mechanical heat resistance and low moldability of the raw material liquid and good moldability, handleability and filling properties. More preferably, those less than 1000 are more preferred. The molecular weight of the component (A) can be measured using a commercially available mass spectrometer.

  In order to obtain good workability, the component (A) preferably has a viscosity at 23 ° C. of less than 100 Pa · s, more preferably less than 50 Pa · s, and even more preferably less than 30 Pa · s. The viscosity here refers to a value measured by an E-type viscometer.

As the component (A), those having a low content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group are preferable from the viewpoint of suppressing coloring, particularly yellowing. What does not contain the compound which has a derivative is preferable. In the present invention, the phenolic hydroxyl group means a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by a benzene ring, naphthalene ring, anthracene ring, etc., and a phenolic hydroxyl group derivative means a hydrogen atom of the above-mentioned phenolic hydroxyl group. A group substituted by an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group or an allyl group, an acyl group such as an acetoxy group, or the like.
From the viewpoint of heat resistance, the component (A) is more preferably a compound containing an isocyanuric acid skeleton represented by the following general formula (III).

(Wherein R ³ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same).

R ^{3 in the} general formula (III) is preferably a monovalent organic group having 1 to 30 carbon atoms from the viewpoint that the heat resistance of the obtained cured product can be further increased. 20 monovalent organic groups are more preferable, and monovalent organic groups having 1 to 10 carbon atoms are even more preferable. Examples of these preferable R ³ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group and the like.

  Preferred specific examples of the compound represented by the above general formula (III) include triallyl isocyanurate, trimethallyl isocyanurate, diallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monophenyl isocyanate. And nurate, tris (2-acryloyloxyethyl) isocyanurate, and the like.

From the viewpoint of high light resistance, the (A) component is preferably an alicyclic compound. Specific examples include vinylcyclohexene, dicyclopentadiene, 1,2,4-trivinylcyclohexane, vinyl norbornene, and divinyl adamantane.
From the viewpoint of a high refractive index, the component (A) is preferably an aromatic compound. Specifically, divinylbenzenes represented by the following general formula (IV), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, oligomers thereof, and bisphenol A diallyl ether In addition, a glycidyl group partially or wholly bonded to an aromatic ring-containing epoxy resin such as bis [4- (2-allyloxy) phenyl] sulfone or phenol novolac resin is preferably substituted with an allyl group.

(In the formula, R ⁴ represents an organic group which may be substituted with monovalent oxygen, nitrogen, sulfur or halogen atom having 1 to 50 carbon atoms, and each R ⁴ may be different or the same. May be good.)
As R ⁴ of the general formula (IV), from the viewpoint that the heat resistance of the obtained cured product can be higher,

It is preferable to have a plurality of aromatic rings.

((B) component)
The component (B) is a compound having a chain and / or cyclic organosiloxane skeleton and having at least one SiH group and at least one epoxy group and / or oxetanyl group in one molecule. (B) The compound contained in a component may be single or multiple.
Examples of the chain organosiloxane compound include the following general formula (V):

(In the formula, each R ⁵ represents a substituent represented by hydrogen or a monovalent organic group having 1 to 50 carbon atoms, and each R ⁵ may be different or the same, 1 is hydrogen, and at least one is a substituent containing an epoxy group and / or an oxetanyl group, and n represents a number of 0 to 1000). From the viewpoint that the heat resistance of the resulting cured product can be higher, R ⁵ in the general formula (V) is preferably a monovalent organic group having 0 to 20 carbon atoms, and has 0 to 15 carbon atoms. It is more preferably a monovalent organic group, and further preferably a monovalent organic group having 0 to 10 carbon atoms. Examples of these preferable R ⁵ include hydrogen group, methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, methoxy group, ethoxy group, vinyl group, allyl group, glycidyl group, cyclohexyl group. Sanyl oxide etc. are mentioned.

  Examples of the cyclic organosiloxane compound include the following general formula (VI):

(Wherein R ⁶ represents hydrogen or an organic group having 1 to 20 carbon atoms, and each R ⁶ may be different or the same, but at least one is hydrogen, and at least one is It is a substituent containing an epoxy group and / or an oxetanyl group.n represents a number of 2 to 10.). Note that R ⁶ in the general formula (VI) is preferably an organic group having 0 to 20 carbon atoms composed of C, H, and O, and more preferably a hydrocarbon group having 0 to 10 carbon atoms. preferable. R ⁶ is particularly preferably a methyl group from the viewpoints of availability and heat resistance, and more preferably a phenyl group from the viewpoint of increasing the refractive index of the cured product. N is preferably a number of 3 to 10.

  The content of the siloxane component contained in the resin skeleton in the curable composition of the present invention is preferably 50 parts by weight or less, more preferably 48% by weight, with respect to 100 parts by weight of the total amount of the composition, 45 It is particularly preferable that the amount is not more than wt%. When the siloxane component is more than 50% by weight, the hardness when cured may not be sufficient and may not be used as an optical material. Here, the siloxane component represents a unit in which a silicon atom and an oxygen atom are directly bonded, such as —Si—O—, that is, a unit composed of one silicon atom and one oxygen atom. Other substituents on the silicon atom are not included in the siloxane component of the present invention.

  The component (B) may contain at least one SiH group in one molecule, but is preferably 2 or more, more preferably 3 or more, and still more preferably 5 or more. When two or more SiH groups are contained in one molecule, a cross-linked density is increased, a cured product having excellent heat resistance and high hardness is obtained.

  The epoxy group and / or oxetanyl group contained in the component (B) is not particularly limited, but an alicyclic epoxy group, a glycidyl group, or an oxetanyl group is preferable from the viewpoint of stability. From the viewpoint of excellent photocationic polymerizability, an alicyclic epoxy group is preferable, and from the viewpoint of improving the toughness of the cured product, an oxetanyl group is preferable.

  The component (B) may contain at least one epoxy group and / or oxetanyl group in one molecule, but is preferably 2 or more, more preferably 3 or more, and still more preferably 5 or more. If there are two or more epoxy groups and / or oxetanyl groups contained in one molecule, a cross-linked density is increased, and a cured product having excellent heat resistance and high hardness can be obtained.

  The molecular weight of the component (B) is not particularly limited, and any one can be suitably used. However, from the viewpoint that the fluidity of the curable composition can be more easily controlled, those having a low molecular weight are preferably used. In this case, the upper limit of the preferable molecular weight is 100,000, more preferably 10,000, and still more preferably 5000. Moreover, from a volatility viewpoint, the minimum of the preferable molecular weight is 50, More preferably, it is 80, More preferably, it is 100.

From the viewpoint of having good compatibility with the component (A), and from the viewpoint that the problem of outgas from the composition that can lower the volatility of the component (B) is less likely to occur, the component (B) is (α ) An organic compound having one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule;
(Β) an organosiloxane compound having at least three SiH groups in one molecule, and (γ) a carbon-carbon having reactivity with at least one epoxy group and / or oxetanyl group in one molecule and a SiH group. A compound that can be obtained by hydrosilylation of a compound having one or more double bonds is preferred.

((Α) component)
Here, as the component (α), the same component (α1) as the compound (A) described above, which is the same as the compound having at least two carbon-carbon double bonds in one molecule, can be used. When the component (α1) is used, the resulting cured product has a high crosslink density and tends to be a cured product having high mechanical strength.

  As the component (α), a compound (α2) having one carbon-carbon double bond in one molecule, which is the component (E) described later, can also be used. When the (α2) component is used, the obtained cured product has low elasticity, and stress is easily reduced.

In addition, an organosiloxane compound (α3) having at least two carbon-carbon double bonds in one molecule can also be used. When the (α3) component is used, the light resistance of the resulting cured product is increased.
Specific examples of the (α3) component include tetramethyldivinyldisiloxane, hexamethyltrivinyltrisiloxane, and cyclic siloxanes containing SiH groups, where the hydrogen atoms of SiH groups are replaced with alkenyl groups such as vinyl groups and allyl groups. And specifically, 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1,3, 5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-trimethylcyclosiloxane, 3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl- , 3,5,7,9,11- compounds such as hexamethylcyclotrisiloxane siloxane.
(Α) The compound contained in the component may be single or plural.

((Β) component)
The (β) component is not particularly limited as long as it is an organosiloxane compound having at least three SiH groups in one molecule, and specific examples include the skeleton described in the (B) component and in one molecule. Those having at least 3 SiH groups.

((Γ) component)
Component (γ) is particularly limited as long as it is a compound having at least one epoxy group and / or oxetanyl group and one or more carbon-carbon double bonds having reactivity with SiH group in one molecule. Not. The compound contained in the component (γ) may be single or plural.
The epoxy group and / or oxetanyl group contained in the component (γ) is not particularly limited, but an alicyclic epoxy group, a glycidyl group, or an oxetanyl group is preferable from the viewpoint of stability. From the viewpoint of excellent photocationic polymerizability, an alicyclic epoxy group is preferable, and from the viewpoint of improving the toughness of the cured product, an oxetanyl group is preferable.

  Specific examples of the component (γ) include vinylcyclohexene oxide, allyl glycidyl ether, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, allyl oxetanyl ether, vinyl oxetanyl ether and the like.

(Preliminary reaction)
The reaction for obtaining the compound (B) from the components (α), (β) and (γ) will be described.

  The mixing ratio of the (α) component, the (β) component, and the (γ) component is not particularly limited as long as two or more SiH groups remain in one molecule, but in the (α) component and the (γ) component. The ratio of the sum of the number of moles of carbon-carbon double bonds contained in (X) and the number of moles of SiH groups (Y) in the component (β) is 1 ≦ Y / X ≦ 30 It is preferable that 1 ≦ Y / X ≦ 10. In the case of 1> Y / X, unreacted alkenyl groups remain in the composition, which causes coloring. In the case of 30 <Y / X, a large amount of (β) component is used. It is not preferable from the viewpoint of increasing.

  In addition, regarding the ratio of the (α) component and the (γ) component, the number of carbon-carbon double bonds in the (α) component is A1, and the number of carbon-carbon double bonds in the compound (γ) is A2. In this case, A1 + A2 = 1 can be selected as appropriate within the range of 0.01 ≦ A1 ≦ 0.99 and 0.01 ≦ A2 <0.99.

  In the case of hydrosilylation, an appropriate catalyst may be used. As the catalyst, for example, the component (D) described later can be used.

The addition amount of the catalyst is not particularly limited, but the lower limit of the preferred addition amount is sufficient with respect to 1 mole of SiH group of the (β) component in order to have sufficient curability and keep the cost of the curable composition relatively low. 10 ⁻¹⁰ mol, more preferably 10 ⁻⁸ mol, and the upper limit of the preferable addition amount is 10 ⁻¹ mol, more preferably 10 ⁻³ mol, relative to 1 mol of SiH group of the component (β).

In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, 2-hydroxy-2-methyl-1 -Acetylene alcohol compounds such as butyne, sulfur compounds such as simple sulfur, amine compounds such as triethylamine, and the like. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount relative to 1 mol of the hydrosilylation catalyst is 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^2. Mol, more preferably 10 mol.

  There are various reaction sequences and methods, but from the viewpoint that the synthesis process is simple, the (α) component, the (β) component, and the (γ) component are subjected to a hydrosilylation reaction in one pot. The method of removing the compound of the reaction is preferable, and from the viewpoint that it is difficult to contain a low molecular weight substance, the hydrosilylation reaction is performed by adding the (γ) component after the (α) component and the (β) component are hydrosilylated. A reaction method is preferred.

The reaction temperature can be variously set. In this case, the lower limit of the preferable temperature range is 30 ° C., more preferably 50 ° C., and the upper limit of the preferable temperature range is 200 ° C., more preferably 150 ° C. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, it is not practical. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required.
Various reaction times and pressures during the reaction can be set as required. The reaction time is not particularly limited. From the economical aspect, it is preferably within 20 hours, more preferably within 10 hours. The pressure is not particularly limited, but is preferably from atmospheric pressure to 5 MPa, more preferably from atmospheric pressure to 2 MPa from the viewpoint that a special apparatus is required and the operation becomes complicated.

  A solvent may be used during the hydrosilylation reaction. Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. The solvent can also be used as a mixed solvent of two or more types. As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, and chloroform are preferable. The amount of solvent to be used can also be set as appropriate.

  After the (α) component, the (β) component, and the (γ) component are hydrosilylated, the solvent and / or the unreacted compound may be removed. Examples of the removal method include vacuum devolatilization. When devolatilizing under reduced pressure, it is preferable to treat at a low temperature. The upper limit of the preferable temperature in this case is 120 ° C, more preferably 100 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

  In order to improve storage stability when preserving (B) component obtained by hydrosilylation reaction of (α) component, (β) component, and (γ) component, an inert gas such as nitrogen or argon Storage at 10 ° C. or lower is preferable in an atmosphere, storage at 0 ° C. or lower is particularly preferable, and storage at −10 ° C. or lower is more preferable.

((C) component)
Component (C) is a photocationic polymerization initiator, and any photocationic polymerization initiator that generates a cationic species or a Lewis acid by active energy rays can be used without any particular limitation. The cationic photopolymerization initiator contained in the component (C) may be used alone or in combination of two or more.

Specific examples of the component (C) include metal fluoroboron complex salts and boron trifluoride complex compounds as described in US Pat. No. 3,379,653; bis (perfluoroalkyls as described in US Pat. No. 3,586,616). Sulfonyl) methane metal salts; aryldiazonium compounds as described in US Pat. No. 3,708,296; aromatic onium salts of group VIa elements as described in US Pat. No. 4,058,400; described in US Pat. Aromatic onium salts of Group Va elements such as: dicarbonyl chelates of Group IIIa to Va elements as described in US Pat. No. 4068091; thiopyrylium salts as described in US Pat. No. 4,139,655; US Pat. No. 4,161,478 MF6 ^- anions (where M is phosphorus, anti Element VIa in the form of selected from mon and arsenic; arylsulfonium complex salts as described in US Pat. No. 4,231,951; aromatic iodonium complex salts and aromatic sulfonium complex salts as described in US Pat. No. 4,256,828; W. R. Bis [4- (diphenylsulfonio) phenyl] sulfide-bishexafluoro as described by Watt et al. In “Journal of Polymer Science, Polymer Chemistry Edition”, Vol. 22, p. 1789 (1984). Metal salts (for example, phosphates, arsenates, antimonates, etc.); aromatic iodonium complex salts and aromatic sulfonium complex salts whose anion is B (C ₆ F ₅ ) ₄ ^— ; diazomethane compounds; sulfonic acid complex salts; triazine compounds, etc. Is exemplified.

  From the viewpoint of availability, arylsulfonium complex salts, aromatic sulfonium or iodonium salts of halogen-containing complex ions, and onium salts of Group II, Group V and Group VI elements are preferred. Some of these salts are FX-512 (3M), UVE-1014 and UVE-1016 (General Electric), KI-85 (Degussa), SP-152 and SP-172 (ADEKA) and Sun Aid SI-60L, SI-80L and SI-100L (Sanshin Chemical Industry Co., Ltd.), WPI113 and WPI116 (Wako Pure Chemical Industries, Ltd.), RHODORSIL PI2074 (Rhodia Co., Ltd.) are available as commercial products.

  From the viewpoint of reactivity, a cationic photopolymerization agent having a maximum absorption wavelength peak in the range of 300 to 450 nm is preferable. When the maximum peak of the absorption wavelength is in the range of 300 to 450 nm, good reactivity can be obtained even when light is irradiated through glass, for example.

The addition amount of the cationic photopolymerization initiator has sufficient curability, and in order to ensure the heat and light resistance of the curable composition, 1 mol of epoxy group and / or oxetanyl group contained in the curable composition. On the other hand, it is preferably 10 ⁻⁸ to 10 ⁻¹ mol, more preferably 10 ⁻⁷ to 10 ⁻² mol.

((D) component)
The thermal hydrosilylation catalyst of component (D) is not particularly limited as long as it has catalytic activity for the hydrosilylation reaction. For example, platinum alone; solid platinum supported on a support such as alumina, silica, carbon black; Chloroplatinic acid; complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc .; platinum-olefin complexes (eg, Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ); platinum-vinylsiloxane complexes (eg, Pt (ViMe ₂ SiOSiMe ₂ Vi) _a , Pt [(MeViSiO) ₄ ] _b ); platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ )) _4); platinum - phosphite complex _{(e.g., Pt [P (OPh) 3} ] 4, Pt [P (OBu) 3] 4) ( in the formula, Me Methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and a and b represent an integer.); Dicarbonyldichloroplatinum; Karlstedt catalyst; platinum-hydrocarbon complex (for example, Platinum-hydrocarbon complexes described in Ashby US Pat. Nos. 3,159,601 and 3,159,662; platinum alcoholate catalysts (eg, described in US Pat. No. 3,220,972 of Lamoreaux). And platinum alcoholate catalyst). In addition, platinum chloride-olefin complexes (eg, the platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946) are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _4. Etc.

  Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.

The amount of component (D) to be added is not particularly limited, but it is preferable with respect to 1 mol of SiH groups in component (B) in order to have sufficient curability and keep the cost of the curable composition relatively low. Is 10 ⁻⁸ to 10 ⁻¹ mol, more preferably 10 ⁻⁷ to 10 ⁻² mol.

  In addition, a cocatalyst can be used in combination with the catalyst. Examples of the cocatalyst include a sulfur-based compound such as simple sulfur, and an amine-based compound such as triethylamine.

The addition amount of the cocatalyst is not particularly limited, but is preferably 10 ⁻² to 10 ² mol, more preferably 10 ⁻¹ to 10 mol, with respect to 1 mol of the hydrosilylation catalyst.

In the bonded substrate of the present invention, the viscosity of the curable composition comprising the component (A) to the component (D) sandwiched between the first substrate and the second substrate is 0.01 to 5 Pa · s. Is preferable, 0.03 to 3 Pa · s is more preferable, and 0.05 to 2 Pa · s is further preferable. By including the viscosity within this range, workability when coating or applying the curable composition is improved, and uniformity and flatness of the film thickness of the curable composition layer between the substrates are improved. There is a tendency.
Moreover, in the bonded substrate of the present invention, the curable composition comprising the component (A) to the component (D) sandwiched between the first substrate and the second substrate was cured using light and heat. The molded product of the resin composition has a storage elastic modulus in a tensile mode of dynamic viscoelasticity measurement of 1700 MPa or more at 23 ° C. and a storage elastic modulus at 100 ° C. of 70 MPa or less. In this respect, there is a good tendency.

  As the bonded substrate of the present invention, a known substrate can be used as long as it is usually used as a semiconductor substrate, but it is particularly preferably selected from a silicon substrate and / or a glass substrate having a thickness of less than 1 mm. In particular, a bonded substrate in which a curable composition composed of components (A) to (D) is sandwiched and cured between a silicon substrate and a glass substrate can be used for an optical semiconductor device such as a CMOS sensor.

  In the bonded substrate of the present invention, the component (E) can be added for the purpose of further improving the flatness and the film thickness uniformity of the resin composition layer. The component (E) will be described below.

((E) component)
(E) A component will not be specifically limited if it is a compound containing the compound which has one carbon-carbon double bond in 1 molecule, For example, the compound which modified | denatured the organic compound, the silicone compound, the organic compound, and the silicone compound is included. Illustrated. When the component (E) is contained, there is an advantage that a flat bonded substrate can be obtained when the substrate is bonded using the composition of the present invention. (E) The compound contained in a component may be single or multiple.

Although it does not restrict | limit especially as a carbon-carbon double bond contained in (E) component, The thing similar to what was demonstrated by the said (A) component can be used.
From the viewpoint of further improving heat resistance, the carbon-carbon double bond contained per gram of component (E) is preferably 1 mmol or more, more preferably 1.5 mmol or more, and 2 mmol or more. It is particularly preferred.

  The component (E) preferably has a molecular weight of less than 2000, and preferably less than 1500 from the viewpoint of high mechanical heat resistance and low moldability of the raw material liquid and good moldability, handleability and filling properties. More preferably, those less than 1000 are more preferred.

  In order to obtain good workability, the component (E) is preferably liquid at room temperature, preferably has a viscosity at 23 ° C. of less than 50 Pa · s, more preferably less than 30 Pa · s, more preferably 10 Pa · s. Those less than s are more preferred. The viscosity here refers to a value measured by an E-type viscometer.

  As the component (E), those having a small content of a phenolic hydroxyl group and / or a compound having a phenolic hydroxyl group derivative are preferable from the viewpoint of suppressing coloring, particularly yellowing. What does not contain the compound which has a derivative is preferable. In the present invention, the phenolic hydroxyl group means a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by a benzene ring, naphthalene ring, anthracene ring, etc., and a phenolic hydroxyl group derivative means a hydrogen atom of the above-mentioned phenolic hydroxyl group. A group substituted by an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group or an allyl group, an acyl group such as an acetoxy group, or the like.

From the viewpoint of high modulus of elasticity and hardness, the amount of component (E) added is that the carbon-carbon double bond derived from component (E) contained in the composition is 1.8 mmol / g or less. Preferably, it is 1.5 mmol / g or less, more preferably 1.3 mmol / g or less. Here, the amount of the carbon-carbon double bond derived from the component (E) contained in the composition is determined by measuring ¹ H-NMR of the composition using the internal standard and comparing the number of protons derived from the vinyl group. Or by calculating from the number of blended parts using the vinyl group amount obtained by measuring ¹ H-NMR of the monomer using the vinyl group amount calculated from the monomer structure or the internal standard.

  From the viewpoint of the brittleness of the cured product, the component (E) is preferably an organic compound. As an example of a preferable organic compound, what was demonstrated by (A) component is mentioned.

  From the viewpoint of light resistance of the cured product, the component (E) is preferably a silicon-containing compound. Specific examples include trimethylvinylsilane, allyltrimethylsilane, diphenylmethylvinylsilane, and allyldiphenylmethylsilane.

  From the viewpoint of increasing the refractive index of the cured product, the component (E) is preferably a silicon-containing compound substituted with an aromatic.

((F) component)
Component (F) is a sensitizer. When the component (F) is contained, sensitivity can be given to light having a high wavelength such as g-line (436 nm), h-line (405 nm), and i-line (365 nm), and the sensitivity of light is improved. Component (F) can be used in combination with the above-mentioned photocationic polymerization initiator to adjust the curability. (F) The compound contained in a component may be single or multiple.

Examples of the component (F) include anthracene compounds and thioxanthone compounds.
Specific examples of the anthracene compound include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-di. Ethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, 9,10-diphenyl-2,6-di- tert-butylanthracene and the like are mentioned. From the viewpoint of availability, anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene, etc. preferable.

  Anthracene is preferable from the viewpoint of excellent transparency of the cured product, and 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-diethoxy from the viewpoint of excellent compatibility with the curable composition. Anthracene and the like are preferable.

  Specific examples of the thioxanthone series include thioxanthone, 2-chlorothioxanthone, 2,5-diethyldioxanthone and the like.

  Component (F) is added in an amount of 0.5 part or less, preferably 0.3 part or less, more preferably 0.2 part or less, relative to 100 parts by weight of the resin. If the amount added is more than 0.5 parts, the heat resistance may decrease.

(Other additives)
(Storage stabilizer)
A storage stabilizer is preferably added for the purpose of improving the storage stability of the curable composition of the present invention. Examples of the storage stabilizer include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide, and these may be used in combination. Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, maleate esters and the like. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide and the like. Examples of nitrogen-containing compounds include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

  Among these storage stabilizers, 1-ethynylcyclohexanol, 3-hydroxy-3-methyl-1-butyne, and dimethyl malate are preferable from the viewpoint of good storage stability and good raw material availability.

The addition amount of the storage stabilizer is preferably in the range of 10 ⁻¹ to 10 ³ mol, more preferably in the range of 1 to 100 mol, with respect to 1 mol of the hydrosilylation catalyst used.

(Anti-aging agent)
An aging inhibitor may be added to the curable composition of the present invention. Examples of the anti-aging agent include citric acid, phosphoric acid, sulfur-based anti-aging agent and the like in addition to the anti-aging agents generally used such as hindered phenol type.

  Various types of hindered phenol-based anti-aging agents such as Irganox 1010 available from BASF are used.

  Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylates, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.

  Moreover, these anti-aging agents may be used independently and may be used together 2 or more types.

(Reactive diluent)
A reactive diluent can be appropriately added to the curable composition of the present invention in order to adjust workability, reactivity, adhesiveness, and strength of the cured product. The compound to be added can be selected according to the curing reaction mode and used without any particular limitation, and a compound having a polymerization group such as an epoxy compound, an oxetane compound, an alkoxysilane compound, or a (meth) acrylate compound is used.

  Specific examples of epoxy compounds and oxetane compounds include novolak phenol type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, cyclohexyl epoxy group-containing organosiloxanes (cyclic, chain-like), glycidyl group-containing organosiloxanes (cyclic, Chain), bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2′-bis (4-glycidyloxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinyl Cyclohexene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohex L) Adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, 1,4-bis {(3-ethyl-3-oxetanyl) methoxy } Methyl} benzene, bis {1-ethyl (3-oxetanyl)} methyl ether, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, etc. be able to.

  Specific examples of the alkoxysilane compound include tetramethoxy (ethoxy) silane and its condensate, methyltrimethoxy (ethoxy) silane and its condensate, dimethyldimethoxy (ethoxy) silane and its condensate.

  Specific examples of (meth) acrylate compounds include allyl (meth) acrylate, vinyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and (meth) acrylic acid. Modified allyl glycidyl ether (manufactured by Nagase ChemteX, trade name: Denacol acrylate DA111), urethane (meth) acrylates, epoxy (meth) acrylates, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Ditrimethylolpropane (meth) tetraacrylate, dipentaerythritol hexa (meth) acrylate, butanediol di (meth) acrylate, nonanediol di (meth) acrylate, polypropylene glycol System (meth) acrylate, bisphenol A di (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, and (meth) acrylate group-containing organosiloxane.

  Although the amount of reactive diluent added can be variously set, the preferred amount added is 1 to 50 parts by weight, more preferably 3 to 25 parts by weight, based on 100 parts by weight of the modified organosiloxane compound. If the addition amount is small, the addition effect does not appear, and if the addition amount is large, the physical properties of the cured product may be adversely affected.

(Adhesion improver)
An adhesion improver can also be added to the curable composition of the present invention. In addition to commonly used adhesives as adhesion improvers, for example, various coupling agents, epoxy compounds, oxetane compounds, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, α-methylstyrene -Vinyl toluene copolymer, polyethyl methyl styrene, aromatic polyisocyanate, etc. can be mentioned.

  An example of the coupling agent is a silane coupling agent. The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesion and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Alkoxysilanes which can be exemplified.

The addition amount of the silane coupling agent can be variously set, but is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, and still more preferably 0 to 100 parts by weight of the modified organosiloxane compound. 0.5 to 5 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the curability and the physical properties of the cured product may be adversely affected.
These coupling agents, silane coupling agents, epoxy compounds, etc. may be used alone or in combination of two or more.

In the present invention, carboxylic acids and / or acid anhydrides can be used in order to enhance the effect of the coupling agent or the epoxy compound, and adhesion can be improved and / or stabilized. Such carboxylic acids and acid anhydrides are not particularly limited,
2-ethylhexanoic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylheimic acid, norbornene dicarboxylic acid, hydrogenated methylnadic acid, maleic acid, acetylenedicarboxylic acid, Examples include lactic acid, malic acid, citric acid, tartaric acid, benzoic acid, hydroxybenzoic acid, cinnamic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalene carboxylic acid, naphthalene dicarboxylic acid, and single or complex acid anhydrides thereof It is done.

  Among these carboxylic acids and / or acid anhydrides, preferred carboxylic acids and / or acid anhydrides include, for example, tetrahydrophthalic acid, methyltetrahydrophthalic acid, and the like in that the properties of the resulting cured product are not easily impaired. Examples thereof include acids and their single or complex acid anhydrides.

  The amount used in the case of using carboxylic acids and / or acid anhydrides can be variously set, but the preferred range of addition amount with respect to 100 parts by weight of the coupling agent and / or epoxy compound is 0.1 to 50 parts by weight, More preferably, it is 1-10 weight part. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the cured product may be adversely affected.

  Further, these carboxylic acids and / or acid anhydrides may be used alone or in combination of two or more.

(Radical inhibitor)
A radical inhibitor may be added to the curable composition of the present invention. Examples of the radical inhibitor include 2,6-di-t-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-t-butylphenol), tetrakis (methylene- Phenol radical inhibitors such as 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, phenyl-β-naphthylamine, α-naphthylamine, N, N′-secondary butyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine, and the like.
Moreover, these radical inhibitors may be used alone or in combination of two or more.

  The curable composition of the present invention includes other colorants, mold release agents, flame retardants, flame retardant aids, surfactants, emulsifiers, leveling agents, anti-fogging agents, ion trapping agents such as antimony-bismuth, thixo Imparting agent, tackifier, infrared absorber, ozone degradation inhibitor, light stabilizer, thickener, antifoaming agent, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity imparting Agents, antistatic agents, radiation blocking agents, nucleating agents, phosphorus peroxide decomposing agents, lubricants, pigments, metal deactivators, thermal conductivity imparting agents, physical property modifiers, etc. It is possible to add in the range which is not.

(Method for adjusting curable composition and curing method)
The preparation method of a curable composition is not specifically limited, It can prepare with various methods. Various components may be mixed and prepared immediately before curing, or may be stored at a low temperature in a one-component state in which all components are mixed and prepared in advance. After mixing all the components, only a part of the functional groups in the composition may be reacted by utilizing reaction control conditions or differences in functional group reactivity. When additives such as thermoplastic resins are used for the purpose of improving physical properties, these additives and a platinum compound as a curing catalyst are mixed and stored in advance, and each predetermined amount is mixed immediately before curing. It may be prepared.

From the viewpoint of obtaining a flat bonded substrate having a high hardness and elastic modulus of the adhesive layer, the carbon-carbon double bond contained in the curable composition of the present invention is 1.0 to 2.7 mmol / g. The amount is preferably in the range of 1.2 to 2.6 mmol / g, more preferably in the range of 1.5 to 2.5 mmol / g. It is particularly preferred. The amount of carbon-carbon double bonds contained in the curable composition was determined by measuring ¹ H-NMR of the composition using an internal standard, comparing the number of protons derived from vinyl groups, or calculating from the monomer structure. it can be determined by or calculated from the compounded part with vinyl amount obtained by ^{1 H-NMR} analysis of the monomer with the vinyl group amount and internal standard.

From the viewpoint that the elastic modulus of the adhesive layer is high and a flat bonded substrate is obtained, the epoxy group and / or oxetanyl group contained in the curable composition of the present invention is 1.0 to 2.4 mmol / g. The amount is preferably in the range, more preferably in the range of 1.2 to 2.4 mmol / g, and more preferably in the range of 1.5 to 2.4 mmol / g. Is particularly preferred. The amount of epoxy group and / or oxetanyl group contained in the curable composition is determined by measuring ¹ H-NMR of the composition using the internal standard, comparing the number of protons derived from the vinyl group, or calculating from the monomer structure. it can be determined by or calculated from the compounded part with vinyl amount obtained by ^{1 H-NMR} analysis of the monomer with the vinyl group amount and internal standard.

  The method of using the curable composition of the present invention is not particularly limited, and can be used by spin coating, slit coating, dispensing potting, or the like. Further, viscosity adjustment with a solvent and surface tension adjustment with a surfactant may be appropriately performed according to the state of the substrate.

Moreover, the resin composition of this invention makes a hardened | cured material by making a crosslinking reaction advance by a light irradiation process and a heating process. As a light source for photocuring, a light source that emits light having an absorption wavelength of a polymerization initiator or a sensitizer to be used may be used. High pressure mercury lamp, metal halide lamp, high power metal halide lamp, xenon lamp, carbon arc lamp, light emitting diode, etc. can be used. The exposure amount is not particularly limited, but a preferable exposure amount range is 1 to 5000 mJ / cm ² , more preferably 1 to 1000 mJ / cm ² . If the exposure is small, it will not cure. If the exposure amount is large, the color may change due to rapid curing. A preferable curing time range is 3 to 120 seconds, and more preferably 10 to 60 seconds.

  The heating temperature in the heating step after the light irradiation is not particularly limited, but is preferably 250 ° C. or lower and 200 ° C. or lower from the viewpoint that the influence on the surrounding low heat-resistant member is small. More preferably it is. Moreover, it is preferable that it is 50 degreeC or more from a viewpoint of reaction time, and it is further more preferable that it is 80 degreeC or more.

  The heating step may be performed at a constant temperature, but the temperature may be changed in multiple steps or continuously as necessary. Rather than carrying out the reaction at a constant temperature, the reaction is preferably carried out while raising the temperature in a multistage manner or continuously in that a uniform cured product without distortion can be easily obtained.

  The pressure during the heating step can also be variously set as necessary, and the reaction can be carried out at normal pressure, high pressure or reduced pressure.

  Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.

(Synthesis Example 1)
In a 500 mL four-necked flask, 200 g of toluene and 95 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixed liquid of 27.64 g of triallyl isocyanurate, 27.64 g of toluene and 1.73 g of a xylene solution of platinum vinylsiloxane complex (containing 0.03 wt% as platinum) was dropped. After completion of dropping, ¹ H-NMR confirmed that the peak due to the allyl group had disappeared, and then a mixture of 67.15 g of vinylcyclohexene oxide and 67.15 g of toluene was added. After the addition, it was confirmed by ¹ H-NMR that the reaction rate of the vinyl group was 95% or more, and the reaction was terminated by cooling. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain “Reactant A”.

Reactant A was obtained by reacting a part of SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with an allyl group of triallyl isocyanurate and a vinyl group of vinylcyclohexene oxide by ¹ H-NMR (mixture) However, it contains a compound having a structure represented by the following formula as a main component). The amount of epoxy group contained by ¹ H-NMR using 1,2-dibromoethane as an internal standard was found to be 3.3 mmol / g.

(Comparative Synthesis Example 2)
Into a 2 L autoclave, 650 g of 1,3,5,7-tetramethylcyclotetrasiloxane and 600 g of toluene were added, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixed solution of 90 g of triallyl isocyanurate, 110 g of toluene and 3.5 g of a xylene solution of platinum vinylsiloxane complex (containing 0.03 wt% as platinum) was added in 10 divided portions. After 6 hours of heating and stirring from the end of dropping, ¹ H-NMR confirmed that the allyl group reaction rate was 95% or more, and the reaction was terminated by cooling. The reaction was terminated by cooling.

Toluene and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane were devolatilized under reduced pressure at 60 ° C. for 2 hours and at 80 ° C. for 2 hours to obtain “Reactant B”. ^{According to 1} H-NMR, this is a reaction of a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane and the allyl group of triallyl isocyanurate (a mixture, but the main component is It was found to contain a compound having a structure represented by:

(Comparative Synthesis Example 3)
A 1000 mL four-necked flask was charged with 60 g of dioxane and 30 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 60 ° C. A mixture of 14 g of divinyltetramethyldisiloxane, 133.5 g of dioxane, and 0.42 g of a dioxane solution of platinum vinylsiloxane complex (containing 0.1 wt% as platinum) was added dropwise over 2 hours. After completion of the dropwise addition, the temperature was raised to 80 ° C., and it was confirmed by ¹ H-NMR that the vinyl group-derived peak had disappeared. Then, 43.5 g of vinylcyclohexene oxide, 144 g of dioxane, a dioxane solution of platinum vinylsiloxane complex (as platinum) 0.96 g of a mixture (containing 0.1 wt%) was added dropwise over 2 hours. After completion of the dropwise addition, it was confirmed by ¹ H-NMR that the SiH group-derived peak had disappeared, and the reaction was terminated by cooling. Dioxane was distilled off under reduced pressure to obtain “Reactant C”. ^{According to 1} H-NMR, this was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with the vinyl group of divinyltetramethyldisiloxane and the vinyl group of vinylcyclohexene oxide (in the mixture). However, it contains a compound having a structure represented by the following formula as a main component). When the amount of epoxy group contained by ¹ H-NMR was determined using p-xylene as an internal standard, it was found to be 4.1 mmol / g.

(Measurement, test)
(viscosity)
Using an EHD viscometer manufactured by Tokyo Keiki Co., Ltd., a 23 ° C. viscosity was measured using an EHD type 1 ° 34 ′ × R24 cone.

(warp)
2 g of the curable composition was applied on a silicon substrate having a thickness of 8 mm and a thickness of 0.5 mm, and a glass substrate having a thickness of 0.75 mm and a thickness of 8 inches from the top was bonded. After the resin spreads on the substrate, UV was irradiated with an integrated light amount of 500 J / cm ³ . Thereafter, the temperature was raised from 60 ° C. to 150 ° C. at 10 ° C./hour, heated at 150 ° C. for 1 hour, and further at 180 ° C. for 0.5 hour to obtain a bonded substrate.

  The obtained bonded substrate was placed on a horizontal base, and gap gauges having different thicknesses were inserted from the edges. Of the gap gauges that could be inserted, the thickest one was warped, and was evaluated and described according to the following criteria.

○: (Warpage) ≦ 500μm
Δ: 500 μm <(warp) ≦ 1000 μm
×: 1000 μm <(warp)
(Shore hardness)
The hardness of the cured product was measured with a type D durometer according to JIS K6253.

(Elastic modulus)
Using a dynamic viscoelastic device DVA-200 manufactured by IT Measurement Control Co., Ltd., measuring temperature -20 to 200 ° C., heating rate 5 ° C./min, strain 0.1%, frequency 10 Hz, distance between chucks 20 mm, tension mode The values of the storage elastic modulus at 23 ° C. and 100 ° C. are described.

(Transmittance)
The light transmittance of the obtained cured product (1 mm thickness) was measured with a spectrophotometer (U-3300, Hitachi), and the transmittance value at 450 nm was described.

(Measurement of functional group amount)
A 300 MHz NMR apparatus manufactured by Varian Technologies Japan Limited was used. The reaction trace in the synthesis example was measured by adding a reaction solution diluted to about 1% with deuterated chloroform to an NMR tube and measuring the peak of unreacted SiH group or methylene derived from unreacted carbon-carbon double bond group. It calculated | required from the peak of the group, and the peak of the methylene group derived from the reactive carbon-carbon double bond group. The amount of functional groups in the synthesis example was determined from the carbon-carbon double bond group value (mmol / g) and the epoxy amount (mmol / g) in terms of dibromoethane or p-xylene.
The amount of functional groups contained in the resin composition was calculated from the number of blended parts by determining the amount of functional groups of each component.

Example 1
A curable composition (Z-1) was prepared with the composition shown in Table 1 (the amount is in parts by weight). Here, a 3 wt% toluene solution was used as the platinum vinylcyclohexane complex. BBI-103 is a diphenyliodonium hexafluoroantimonate compound manufactured by Midori Chemical Co., Ltd., and 50 wt% diethylene glycol dimethyl ether solution and 9,10-dipropoxyanthracene adjusted to 25 wt% diethylene glycol dimethyl ether solution were used. The composition (Z-1) thus obtained was poured into a cell prepared by sandwiching a 1 mm-thick silicone rubber sheet as a spacer between two glass plates, and then irradiated with UV at an integrated light amount of 500 J / cm ³ . Thereafter, the temperature was raised from 60 ° C. to 150 ° C. at 10 ° C./hour in a hot air circulation dryer, and heating was performed in air at 150 ° C. for 1 hour. After cooling, the glass was removed from the glass and further heated in air at 180 ° C./0.5 hours to obtain a cured product for evaluation. This cured product was used for Shore hardness, elastic modulus, and permeability evaluation. Next, 2 g of the composition (Z-1) was applied on a silicon substrate having a thickness of 8 mm and a thickness of 8 mm, and a glass substrate having a thickness of 0.75 mm and a thickness of 8 inches from the top. Pasted together. After the resin spreads on the substrate, UV was irradiated with an integrated light amount of 500 J / cm ³ . Thereafter, the temperature was raised from 60 ° C. to 150 ° C. at 10 ° C./hour in a hot air circulation dryer, and heated in air at 150 ° C. for 1 hour and further at 180 ° C. for 0.5 hour to obtain a bonded substrate. . The warpage evaluation was performed on this bonded substrate.

(Example 2, Comparative Examples 1-2)
In the same manner as in Example 1, a curable composition was prepared according to the composition shown in Table 1, and a cured product for evaluation and a bonded substrate were prepared and evaluated.

(Comparative Example 3)
60 parts of "Reactant B" obtained in Comparative Synthesis Example 2, 40 parts of triallyl isocyanurate, A-187 (manufactured by Momentive Performance Materials, epoxy silicone) platinum vinylcyclohexane complex in 3 wt% toluene solution 0.1 Part, 0.1 part of 1-ethynyl-1-cyclohexanol was mixed and stirred to obtain a composition. Thereafter, a curable composition was prepared in the same manner as in Example 1, and a cured product for evaluation and a bonded substrate were prepared and evaluated.

(Comparative Example 4)
To 76.7 parts of “Reactant C” obtained in Comparative Synthesis Example 3, 10 parts of OXT-212 (manufactured by Toagosei Co., Ltd., oxetane compound), KBM303 (manufactured by Shin-Etsu Chemical Co., Ltd., epoxy silicone compound) 10 Part, Irgacure 250 (manufactured by BASF, photocationic polymerization initiator) 2.6 parts, and Irgacure 127 (manufactured by BASF, sensitizer) 0.7 parts were mixed and stirred to obtain a composition. Thereafter, a curable composition was prepared in the same manner as in Example 1, and a cured product for evaluation and a bonded substrate were prepared and evaluated.

(Comparative Example 5)
About the curable composition (Z-1) obtained in Example 1, the viscosity was adjusted so that a viscosity might be set to 20 Pa.s in the hot-air circulation type oven set to 40 degreeC (Z-2). About the curable composition (Z-2) after adjusting the viscosity, 2 g of the composition (Z-2) was applied on a silicon substrate having a thickness of 8 mm and a thickness of 0.5 mm, and glass having a thickness of 0.75 mm and a thickness of 8 inches from the top. The substrates were bonded together, but even after 1 hour or more had passed, the resin did not spread on the substrates and the bonded substrates could not be produced.

(Comparative Example 6)
For the curable composition (Z-1) obtained in Example 1, 2 g of the composition (Z-1) was applied on a silicon substrate having a thickness of 8 mm and a thickness of 0.5 mm. A 75 mm glass substrate was bonded. After the resin spreads and spreads on the substrate, the temperature is raised from 60 ° C. to 150 ° C. at 10 ° C./hour in a hot air circulation dryer without UV irradiation, at 150 ° C. for 1 hour, and further at 180 ° C. Heated in air for 5 hours to obtain a bonded substrate. The warpage evaluation was performed on this bonded substrate.

As shown in Table 2, when the curable composition having the characteristics of the present invention is used, the application property and transmittance are high, the flatness is excellent, the elastic modulus and hardness of the adhesive layer are high, and the workability is excellent. A laminated substrate can be obtained.

Claims (11)

The composition having the following components (A) to (D) as essential components, having a solution viscosity at 23 ° C. of 5 Pa · s or less, includes a first substrate having a thickness of less than 1 mm and a second substrate having a thickness of less than 1 mm. A curable resin composition layer cured by light irradiation and application of heat of 80 ° C. or more after being sandwiched between them is formed, and the tensile storage elasticity of the curable resin composition layer at 23 ° C. A bonded substrate having a modulus of 1700 MPa or more and a tensile storage modulus at 100 ° C. of 70 MPa or less.
(A) A compound having at least two carbon-carbon double bonds in one molecule (B) containing a chain and / or cyclic polysiloxane skeleton, at least one SiH group in one molecule, and an epoxy group And / or compound having at least one oxetanyl group (C) photocationic polymerization initiator (D) thermal hydrosilylation catalyst The molecular weight of (A) component is 2000 or less, The bonded substrate of Claim 1 characterized by the above-mentioned. Furthermore, the compound which has one carbon-carbon double bond in one molecule as (E) component is contained, The bonded substrate as described in any one of Claims 1-2 characterized by the above-mentioned. The carbon-carbon double bond contained in the composition is 1.0 to 2.7 mmol / g, the epoxy group and / or the oxetanyl group is 1.0 to 2.4 mmol / g, and is derived from the component (E) The bonded substrate according to claim 3, wherein the amount of carbon-carbon double bonds is in the range of 0.01 to 1.8 mmol / g. The bonded substrate according to any one of claims 1 to 4, wherein an isocyanuric acid ring structure is contained in the composition. The bonded substrate according to any one of claims 1 to 5, wherein the component (B) uses a hydrosilylation reaction product of the following compounds (α) to (γ).
(Α) Organic compound having one or more carbon-carbon double bonds having reactivity with SiH group in one molecule (β) Organosiloxane compound (γ) 1 having at least three SiH groups in one molecule Compound having at least one epoxy group and / or oxetanyl group and one or more carbon-carbon double bonds having reactivity with SiH group in the molecule The epoxy group and / or oxetanyl group contained in the component (B) is an alicyclic epoxy group, oxetanyl group, or glycidyl group, according to any one of claims 1 to 6. Bonded substrate. (C) A component is an onium salt, The bonded substrate as described in any one of Claims 1-7 characterized by the above-mentioned. Furthermore, a sensitizer is contained as (F) component, The bonded substrate as described in any one of Claims 1-8 characterized by the above-mentioned. The bonded substrate according to any one of claims 1 to 9, wherein the substrate is selected from a silicon substrate and / or a glass substrate.   A semiconductor product incorporating a component obtained by dicing the bonded substrate according to any one of claims 1 to 10.