Resin composition, cured product, adhesive composition, and optical fiber array

Abstract

Provided is a resin composition having a low refractive index and good heat resistance such as reflow resistance. A resin composition contains (A1) a cyclic siloxane compound having a reactive functional group, (A2) a linear siloxane compound having a reactive functional group, and (B) a polymerization initiator. In addition, (A1) the cyclic siloxane compound having a reactive functional group is preferably an epoxy-modified cyclic siloxane compound having two or four epoxy groups. In addition, (A2) the linear siloxane compound having a reactive functional group preferably has a glycidyl ether structure at both ends.

Description

Technical Field

[0001] This invention relates to a resin composition, a cured material, an adhesive composition, and an optical fiber array. Background Technology

[0002] In recent years, the challenge has been the rapid increase in communication speeds and the need to cope with the surge in communication volume. One solution to this problem is silicon photonics, which combines optical communication technology with existing electrical communication technologies.

[0003] Silicon photonics is a technology that integrates optical waveguides, optical switches, optical modulators, optical receivers and other components on a silicon substrate. It is a technology that integrates optical devices and electronic circuits into optical integrated circuits to realize small, high-function optical devices.

[0004] Previously, optical adhesives have been required to have optical properties such as low refractive index or high transparency. On the other hand, in silicon photonics, multiple reflow processes at 200°C to 260°C are sometimes performed in solder packaging. Therefore, in recent years, in order to use optical adhesives for silicon photonics, in addition to optical properties, reflow resistance is also required.

[0005] Common methods for reducing refractive index include lowering the glass transition temperature of the resin composition or reducing the crosslinking density of the polymer. However, these methods often compromise heat resistance while lowering the refractive index, making it difficult to balance low refractive index with good reflow resistance. Additionally, methods using fluorine compounds are known for reducing refractive index. However, fluorine compounds exhibit a very stable structure, making them difficult to decompose in the environment, raising concerns about environmental impact and gradually restricting their use.

[0006] As a method for fixing optical fibers onto silicon chips, optical coupling adhesives are typically used. In silicon photonics, solder packaging requires multiple reflow processes at 200°C to 260°C. Regarding optical adhesives, the adhesion after the reflow process is rarely considered.

[0007] For example, Patent Document 1 describes a low-refractive-index adhesive containing an acrylic matrix resin and porous hollow resin particles. While Patent Document 1 focuses on porous hollow resin particles in terms of adhesion and transparency, it does not describe a reflow process or heat resistance.

[0008] Furthermore, Patent Document 2 describes the use of compounds containing aromatic rings and reactive silicon-containing groups in adhesive compositions for optical communication that exhibit excellent adhesion, moisture resistance, and low refractive index. However, if a large amount of resin material containing aromatic rings is used, the refractive index becomes high, thus only a refractive index exceeding 1.46, which is typically used as a raw material for optical fibers, can be obtained.

[0009] [Existing technical documents]

[0010] [Patent Literature]

[0011] Patent Document 1: Japanese Patent Application Publication No. 2011-037978

[0012] Patent Document 2: Japanese Patent Application Publication No. 2017-061599 Summary of the Invention

[0013] [The problem the invention aims to solve]

[0014] Given the wide range of applications for resin compositions, there is a need for a resin composition with excellent optical properties or heat resistance.

[0015] For example, a resin composition with low refractive index and excellent reflow resistance is sought.

[0016] The present invention was made in view of the aforementioned issues, and its object is to provide a resin composition with low refractive index and good heat resistance such as reflow resistance, a cured form of the resin composition, and an adhesive composition.

[0017] Another object of the present invention is to provide an optical fiber array using an adhesive composition with low refractive index and good heat resistance, such as reflow resistance.

[0018] [Technical means to solve the problem]

[0019] This invention relates to the resin compositions, curing materials, adhesive compositions, and fiber arrays shown below.

[0020] [1] A resin composition comprising: (A1) Cyclic siloxane compounds with reactive functional groups, (A2) Straight-chain siloxane compounds with reactive functional groups, and (B) Polymerization initiator.

[0021] [2] According to the resin composition described in [1], wherein the (A1) cyclic siloxane compound having a reactive functional group has two or more of the reactive functional groups.

[0022] [3] According to the resin composition described in [1] or [2], wherein the (A1) cyclic siloxane compound having a reactive functional group has a cationic polymerizable group.

[0023] [4] The resin composition according to any one of [1] to [3], wherein the (A1) cyclic siloxane compound having a reactive functional group is an epoxy-modified cyclic siloxane compound having two or four epoxy groups.

[0024] [5] The resin composition according to any one of [1] to [4], wherein the (A2) linear siloxane compound having a reactive functional group has one or more cationic polymerizable groups in the molecule.

[0025] [6] The resin composition according to any one of [1] to [5], wherein the (A2) linear siloxane compound having reactive functional groups has glycidyl ether structures at both ends.

[0026] [7] The resin composition according to any one of [1] to [6], wherein the mass ratio of the cyclic siloxane compound having a reactive functional group (A1) to the linear siloxane compound having a reactive functional group (A2) is 95:5 to 1:99.

[0027] [8] The resin composition according to any one of [1] to [7] further comprises (C) an inorganic filler.

[0028] [9] According to the resin composition described in [8], wherein when the total amount of the resin composition is set to 100 parts by mass, the content of the inorganic filler (C) is 0.1 parts by mass to 80 parts by mass.

[0029]

[10] According to the resin composition described in [8] or [9], wherein the average particle size of the inorganic filler (C) is 0.1 μm to 5.0 μm.

[0030]

[11] The resin composition according to any one of [1] to

[10] further comprises (D) oxetane compound.

[0031]

[12] A cured product is a cured product of the resin composition described in any one of [1] to

[11] .

[0032]

[13] The hardened material described in

[12] has a refractive index of 1.47 or less at a wavelength of 1310 nm.

[0033]

[14] The hardened material described in

[12] or

[13] , wherein the hardened material has a transmittance of 90% or more at a thickness of 100 μm and a wavelength of 1310 nm.

[0034]

[15] The hardened material described in any one of

[12] to

[14] , wherein the rate of decrease in adhesion strength before and after the reflow process, as expressed by the following formula (1), is 74% or less.

[0035] [Formula 1]

[0036]

[16] An adhesive composition comprising the resin composition described in any one of [1] to

[11] , and

[0037] Used for joining optical components.

[0038]

[17] The adhesive composition described in

[16] is used to fix an optical fiber in a groove formed in an optical waveguide element.

[0039]

[18] The adhesive composition described in

[16] or

[17] is used for optical path coupling of optical fiber to optical waveguide element.

[0040]

[19] The adhesive composition according to any one of

[16] to

[18] is used to simultaneously fix the optical fiber in a groove formed in the optical waveguide element and to optically couple the optical fiber to the optical waveguide element.

[0041]

[20] An optical fiber array comprising an adhesive composition according to any one of

[16] to

[19] , an optical fiber, and an optical waveguide element, wherein the optical fiber is optically coupled to the optical waveguide element through the adhesive composition.

[0042] [The effects of the invention]

[0043] The present invention provides a resin composition with low refractive index and good heat resistance such as reflow resistance, a cured form of the resin composition, and an adhesive composition.

[0044] In addition, the present invention provides an optical fiber array using an adhesive composition with low refractive index and good heat resistance, such as reflow resistance. Attached Figure Description

[0045] [ Figure 1 [This is an exploded 3D view of the optical waveguide module.]

[0046] [ Figure 2 [This is an enlarged view of the area near the connection.]

[0047] [ Figure 3 [ ] is a side view showing the state of the optical fiber fixed to the optical waveguide element.

[0048] [ Figure 4 ]yes Figure 3 AA cross-section view. Detailed Implementation

[0049] Hereinafter, embodiments of the present invention (hereinafter referred to as this embodiment) will be described.

[0050] This embodiment relates to a resin composition, a cured form of the resin composition, an adhesive composition comprising the resin composition, and an optical fiber array.

[0051] [definition]

[0052] In this application specification, ○ to △ (e.g., ○ parts by mass to △ parts by mass) means more than ○ and less than △ (more than ○ parts by mass and less than △ parts by mass).

[0053] In addition, in this application specification, the terms "comprising" or "containing" mean that the defined structural element is included, but do not exclude the existence of other structural elements.

[0054] [Resin Composition]

[0055] The resin composition of this embodiment comprises (A1) a cyclic siloxane compound having reactive functional groups, (A2) a linear siloxane compound having reactive functional groups, and (B) a polymerization initiator.

[0056] In addition, cyclic siloxane compounds with reactive functional groups (A1) and linear siloxane compounds with reactive functional groups (A2) are sometimes collectively referred to as "(A) siloxane compounds".

[0057] (A1) Cyclic siloxane compounds with reactive functional groups

[0058] The resin composition of this embodiment contains (A1) a cyclic siloxane compound having a reactive functional group (hereinafter also referred to as "(A1) component" or "(A1) cyclic siloxane compound").

[0059] (A1) If the component is a cyclic siloxane compound having more than one reactive functional group in one molecule, there is no particular limitation.

[0060] As a component (A1), it can be used alone or in combination with two or more.

[0061] The term "reactive functional group" refers to a functional group that can react with the functional groups of the compounds contained in the resin composition of this embodiment.

[0062] There are no particular limitations on reactive functional groups, but examples include: epoxy group, oxetyl group, glycidyl group, alkoxysilyl group, and vinyl ether group.

[0063] (A1) If the number of reactive functional groups in each molecule of the component is 1 or more, there is no particular limitation. From the viewpoint of optical properties or heat resistance, ease of obtaining raw materials or reactivity, it can be 2 or more, preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4, and particularly preferably 2 or 4.

[0064] Cyclic siloxane compounds are compounds that have a cyclic siloxane skeleton based on siloxane bonds (-Si-O-Si-).

[0065] The number of Si-O units forming the cyclic siloxane framework (equal to the number of silicon atoms forming the siloxane ring) is not particularly limited, but from the viewpoints of optical properties or heat resistance, ease of obtaining raw materials or reactivity, it is preferably 2 to 15, more preferably 3 to 10, and even more preferably 3 to 8, and particularly preferably 3 to 6.

[0066] (A1) The preferred component has a cationic polymerizable group as a reactive functional group that bonds to the cyclic siloxane backbone. A cationic polymerizable group refers to a functional group that undergoes chain polymerization in the presence of a cation.

[0067] The (A1) component has cationic polymerizable groups that are bonded to the cyclic siloxane backbone, which can reduce hardening shrinkage while maintaining heat resistance.

[0068] Examples of cationic polymerizable groups include: epoxy group, glycidyl group, oxetyl group, and vinyl ether group.

[0069] Furthermore, although there are no particular limitations, from the viewpoint of reducing the refractive index, the cationic polymerizable group is preferably a functional group that does not have an aromatic ring.

[0070] From the viewpoint of optical properties or heat resistance, ease of obtaining raw materials or storage stability of the composition, the cationic polymerizable group of component (A1) is preferably epoxy group.

[0071] The epoxy group is a group having an oxetine structure and is a substituent having a 3-membered ring (oxetine ring) containing two carbon atoms and one oxygen atom.

[0072] When the cationic polymerizable group is an epoxy group, the epoxy group can be either alicyclic or non-alicyclic.

[0073] From the viewpoint of achieving excellent transparency, the epoxy group is preferably an alicyclic epoxy group.

[0074] Alicyclic epoxy groups have an oxidized cycloalkene (cycloalkene oxide) structure as the alicyclic skeleton.

[0075] Oxidized cyclic olefins have an aliphatic ring and an epoxy group consisting of two adjacent carbon atoms and an oxygen atom constituting the aliphatic ring. Oxidized cyclic olefin structures can be obtained, for example, by epoxidizing cyclic olefins with oxidizing agents such as peroxides.

[0076] The alicyclic skeleton of the alicyclic epoxy group is not particularly limited, and examples include cyclopropane skeleton, cyclobutane skeleton, cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, etc., with cyclohexane skeleton being preferred.

[0077] The non-alicyclic epoxy group is an epoxy group other than the alicyclic epoxy group. Examples of groups containing a non-alicyclic epoxy group include glycidyl group and glycidyloxypropyl group (preferably 3-glycidyloxypropyl group).

[0078] In component (A1), the epoxy group can be directly bonded to the cyclic siloxane skeleton, or it can be bonded to the cyclic siloxane skeleton via a linker group.

[0079] The linking group can be any divalent group, for example: alkylene groups (-(CH2)). n - (n is an integer greater than or equal to 0), ether bonds (-O-), and combinations thereof.

[0080] Furthermore, the epoxy groups are close to the cyclic siloxane backbone, which tends to produce a dense cured product when the resin composition is cured, resulting in excellent heat resistance (reflow resistance).

[0081] Therefore, when the epoxy group is bonded to the cyclic siloxane skeleton via a linker, the number of atoms present between the epoxy group and the cyclic siloxane skeleton is preferably 4 or less, more preferably 2 or less.

[0082] The weight average molecular weight of component (A1) is preferably 200 to 3,000, more preferably 300 to 2,000, and particularly preferably 400 to 1,000.

[0083] If the weight-average molecular weight of component (A1) is within the range described, the viscosity of the resin composition becomes appropriate, and the balance of the optical properties or heat resistance of the cured product becomes good.

[0084] Furthermore, the weight-average molecular weight in this specification refers to the value calculated by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.

[0085] The functional group equivalent (g / mol) of component (A1) is not particularly limited, but from the viewpoint of reactivity, it is preferably 50 to 1,000, more preferably 100 to 500, and particularly preferably 150 to 400.

[0086] Furthermore, the epoxy equivalent in this specification refers to the value measured according to Japanese Industrial Standards (JIS) K7236.

[0087] (A1) The content of component (A1) in the resin composition is not particularly limited. From the viewpoint of improving reflow resistance, when the total amount of the resin composition is set to 100 parts by mass, it is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, more preferably 2.0 parts by mass or more, and particularly preferably 5 parts by mass or more.

[0088] Furthermore, from the viewpoint of having a low refractive index and high transparency, when the total amount of the resin composition is set to 100 parts by mass, the content of component (A1) in the resin composition is preferably 95 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less, and particularly preferably 15 parts by mass or less.

[0089] (A1) The preferred component is a liquid at 25°C, but it can also be a solid at room temperature.

[0090] From the viewpoint of the preparation of the resin composition and its dispensing properties, the viscosity of component (A1) at 25°C is preferably 10 mPa·s to 10,000 mPa·s, more preferably 20 mPa·s to 8,000 mPa·s, and particularly preferably 50 mPa·s to 5,000 mPa·s.

[0091] Furthermore, unless otherwise specified, the viscosity in this instruction manual is expressed using values ​​measured in accordance with Japanese Industrial Standard JIS K6833. Specifically, it can be determined by using a Type E viscometer at a rotation speed of 10 rpm. There are no particular limitations on the machine, rotor, or measurement range used.

[0092] As a component (A1), for example, a compound represented by the following general formula (1) can be used.

[0093] [Chemistry 1]

[0094] (where R) 1 or R 2 The R group represents a glycidyl group, an epoxy group, or a hydrocarbon group with 1 to 6 carbon atoms, and n represents an integer from 3 to 10; multiple R groups may exist in the formula. 1 R 2They can be the same or different; among them, there are multiple R. 1 or R 2 (Among them, at least two are glycidyl groups or organic groups containing cyclohexyl epoxide)

[0095] Examples of compounds containing epoxy groups as component (A1) include: 2,4-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6,8,8-hexamethyl-cyclotetrasiloxane, 4,8-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,2,4,6,6,8-hexamethyl-cyclotetrasiloxane, 2,4-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-6,8-dipropyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 4,8-bis[2-(3- [2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,8-tris[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6,8-pentamethyl-cyclotetrasiloxane, 2,4,8-tris[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-6-propyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,6,8-tetra[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,8-tetramethyl-cyclotetrasiloxane.

[0096] There are no particular limitations on commercially available products when the (A1) component is a cyclic siloxane compound with an epoxy group. Examples include: KR-470 (functionality 4) or X-40-2670 (functionality 4) and X-40-2678 (functionality 2) (all manufactured by Shin-Etsu Chemical Co., Ltd.) as cyclic siloxane compounds with an alicyclic epoxy group; or X-40-2701 (functionality 4) (manufactured by Shin-Etsu Chemical Co., Ltd.), X-40-2728 (functionality 2) (manufactured by Shin-Etsu Chemical Co., Ltd.), and EP-3400L (functionality 4) (manufactured by ADEKA Co., Ltd.) as cyclic siloxane compounds with a non-alicyclic epoxy group, i.e., a glycidyl group.

[0097] (A1) The preferred components are these epoxy-modified cyclic siloxane compounds having two or four epoxy groups.

[0098] In addition, any one of these components (A1) may be used, or two or more may be used together.

[0099] (A1) The epoxy equivalent (g / mol) of the cyclic siloxane compound is not particularly limited, but from the viewpoint of reactivity, it is preferably 50 to 1000, more preferably 100 to 500, and even more preferably 150 to 400. Furthermore, in this specification, the epoxy equivalent can be determined according to JIS K7236.

[0100] (A1) The weight-average molecular weight of the cyclic siloxane compound is not particularly limited, but is preferably 200 to 3000, more preferably 300 to 2000, and even more preferably 400 to 1000. When the weight-average molecular weight of the (A1) cyclic siloxane compound is within the range described, the viscosity of the composition becomes suitable, and the workability is improved. Furthermore, in this specification, the weight-average molecular weight can be calculated by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.

[0101] (A1) The cyclic siloxane compound is preferably a liquid at room temperature (25°C), but it can also be a solid. From an operational point of view, the viscosity of the (A1) cyclic siloxane compound at 25°C is preferably 10 mPa·s to 30000 mPa·s. Furthermore, in this specification, the viscosity can be measured according to Japanese Industrial Standard JIS K6833. Specifically, the viscosity can be determined by using an E-type viscometer at a rotation speed of 10 rpm. There are no particular limitations on the machine, rotor, or measurement range used in the measurement.

[0102] (A2) Straight-chain siloxane compounds with reactive functional groups

[0103] The resin composition of this embodiment contains (A2) a linear siloxane compound having a reactive functional group (hereinafter also referred to as "(A2) component" or "(A2) linear siloxane compound").

[0104] (A2) If the component is a linear siloxane compound having more than one reactive functional group in one molecule, there is no particular limitation.

[0105] As a component (A2), it can be used alone or in combination with two or more.

[0106] The reactive functional groups of component (A2) are the same as those of component (A1) and are not particularly limited. Examples include epoxy, glycidyl, oxetyl, alkoxysilyl, vinyl ether, and alkoxy groups.

[0107] Furthermore, the reactive functional group of component (A2) is preferably a cationic polymerizable group. A cationic polymerizable group is a functional group that undergoes chain polymerization in the presence of a cation.

[0108] The (A2) component has cationic polymerizable groups that are bonded to the linear siloxane backbone, which can reduce hardening shrinkage while maintaining low refractive index.

[0109] Examples of cationic polymerizable groups include: epoxy group, glycidyl group, oxetyl group, and vinyl ether group.

[0110] Furthermore, although there are no particular limitations, from the viewpoint of reducing the refractive index, the cationic polymerizable group is preferably a functional group that does not have an aromatic ring.

[0111] (A2) The number of reactive functional groups in each molecule of the component is not particularly limited if it is 1 or more. From the viewpoint of optical properties or heat resistance, ease of obtaining raw materials or reactivity, it can be 2 or more, preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4, and particularly preferably 2.

[0112] Straight-chain siloxane compounds refer to compounds that have a straight-chain siloxane skeleton based on siloxane bonds (-Si-O-Si-).

[0113] The number of Si-O units forming a linear siloxane framework (equal to the number of silicon atoms forming the siloxane chain) is not particularly limited, but from the viewpoints of optical properties or heat resistance, ease of obtaining raw materials or reactivity, it is preferably 2 to 50, more preferably 3 to 40, even more preferably 5 to 30, and particularly preferably 10 to 20.

[0114] From the viewpoint of optical properties, heat resistance, and adhesion, the cationic polymerizable group of component (A2) is preferably an epoxy group.

[0115] (A2) The preferred component is one or more epoxy groups within the molecule.

[0116] In the case of cationic polymerizability of epoxy groups, similar to component (A1), the epoxy group can be either alicyclic or non-alicyclic.

[0117] From the viewpoint of achieving excellent transparency, the epoxy group is preferably an alicyclic epoxy group.

[0118] In component (A2), the epoxy group can be directly bonded to the linear siloxane skeleton, or it can be bonded to the linear siloxane skeleton via a linker group.

[0119] The linking group can be any divalent group, for example: alkylene groups (-(CH2)). n - (n is an integer greater than or equal to 0), ether bonds (-O-), and combinations thereof.

[0120] Furthermore, the epoxy groups are close to the linear siloxane backbone, which tends to produce a dense cured product when the resin composition is cured, resulting in excellent heat resistance (reflow resistance).

[0121] Therefore, when the epoxy group is bonded to the linear siloxane skeleton via a linker, the number of atoms present between the epoxy group and the linear siloxane skeleton is preferably 4 or less, more preferably 2 or less.

[0122] The weight average molecular weight of component (A2) is preferably 200 to 10,000, more preferably 200 to 8,000, and particularly preferably 400 to 6,000.

[0123] If the weight average molecular weight of component (A2) is within the range described, the viscosity of the resin composition becomes appropriate, and the balance of the optical properties or heat resistance of the cured product becomes good.

[0124] The functional group content (g / mol) of component (A2) is not particularly limited, but from the viewpoint of reactivity, it is preferably 300 to 5,000, more preferably 350 to 3,000, even more preferably 400 to 2,700, and particularly preferably 400 to 1,500.

[0125] (A2) The content of component in the resin composition is not particularly limited. From the viewpoint of having low refractive index and high transparency, when the total amount of the resin composition is set to 100 parts by mass, it is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, and particularly preferably 30 parts by mass or more.

[0126] Furthermore, from the viewpoint of improving reflow resistance, when the total amount of the resin composition is set to 100 parts by mass, the content of component (A2) in the resin composition is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, and particularly preferably 25 parts by mass or less.

[0127] (A2) The preferred component is a liquid at 25°C, but it can also be a solid at room temperature.

[0128] From the viewpoint of the preparation of the resin composition and its dispensing properties, the viscosity of component (A2) at 25°C is preferably 1 mPa·s to 500 mPa·s, more preferably 2 mPa·s to 300 mPa·s, and particularly preferably 5 mPa·s to 100 mPa·s.

[0129] As an example of (A2) component being a linear siloxane compound having an epoxy group, linear siloxane compounds having an epoxy group at the end can be cited, for example.

[0130] The term "linear siloxane compound with an epoxy group at the end" refers to a compound that has an alicyclic epoxy group or a non-alicyclic epoxy group at the end of the main chain formed by siloxane bonds.

[0131] (A2) The component only needs to have an epoxy group at at least one end of the main chain, preferably at all ends of the main chain (two ends of the main chain in the case of no branching).

[0132] (A2) In addition to the end of the main chain, the component may also have epoxy groups in the side chain, preferably only at the end of the main chain.

[0133] From the viewpoint of optical properties and adhesion, component (A2) is particularly preferred to have glycidyl ether structures at both ends.

[0134] As a component (A2), for example, a compound represented by the following general formula (2) may be used.

[0135] [Chemistry 2]

[0136] In general formula (2), R 4 ~R 7 and R 9 ~R 12 Each can be independently represented by a hydrocarbon group or an organic group containing a glycidyl group; R 3 and R 8 Each of these groups independently represents an organic group containing a glycidyl group; m represents -[Si(R 5 (R) 11 The )O]- represents the number of moles of siloxane units in one molecule, and is a number from 0 to 3000; n represents -[Si(R 6 (R) 10 The molar number of siloxane units in one molecule represented by [O] is a number ranging from 0 to 3000.

[0137] (A2) Examples of linear siloxane compounds having alicyclic or non-alicyclic epoxy group at the end are not particularly limited, such as modified silicone oil.

[0138] There are no particular limitations on commercially available modified silicone oils. Examples include: X-22-169B and X-22-169AS, which are modified silicone oils with alicyclic epoxy groups at both ends; X-22-163, KF-105, X-22-163A, X-22-163B, and X-22-163C, which are modified silicone oils with epoxy groups at both ends; X-22-2046 and KF-102, which are modified silicone oils with alicyclic epoxy groups in the side chain; X-22-343, KF-101, KF-1001, and X-22-2000, which are modified silicone oils with epoxy groups in the side chain; and X-22-9002, which is a modified silicone oil with epoxy groups at both ends and in the side chain (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0139] (A2) The preferred component is modified silicone oil.

[0140] In addition, (A2) may use any one of these, or two or more of them together.

[0141] (A2) The epoxy equivalent (g / mol) of the linear siloxane compound is not particularly limited, but from the viewpoint of reactivity, it is preferably 100 to 4000, more preferably 120 to 2000, and even more preferably 150 to 1000.

[0142] (A2) The weight average molecular weight of the linear siloxane compound is not particularly limited, but is preferably 200 to 10,000, more preferably 200 to 8,000, and even more preferably 400 to 6,000. When the weight average molecular weight of the linear siloxane compound (A2) is within the range described, the viscosity of the composition becomes suitable and the workability is improved.

[0143] (A2) The linear siloxane compound is preferably a liquid at room temperature (25°C), but it can also be a solid. From an operational point of view, the viscosity of the (A2) linear siloxane compound at 25°C is preferably 1 mPa·s to 500 mPa·s, more preferably 2 mPa·s to 300 mPa·s, and even more preferably 5 mPa·s to 100 mPa·s.

[0144] The mixing ratio of component (A1) and component (A2)

[0145] In the resin composition, the (A) siloxane compound, the (A1) cyclic siloxane compound with reactive functional groups helps to reduce the refractive index and improve heat resistance.

[0146] In addition, (A2) linear siloxane compounds with reactive functional groups help to reduce the crosslinking density of the hardened material, thereby reducing the refractive index and improving transparency.

[0147] Therefore, (A) siloxane compounds contain both (A1) and (A2) components.

[0148] At this time, in the siloxane compound (A), the ratio (mass ratio) of component (A1) to component (A2) is 95:5 to 1:99, and can be 85:15 to 5:95, 75:25 to 15:85, 70:25 to 25:75, 65:35 to 35:65, 60:40 to 30:70, 55:45 to 25:75, or 50:50 to 20:80.

[0149] Furthermore, when the total amount of the resin composition is set to 100 parts by mass, the content of component (A) in the resin composition of this embodiment is preferably 5 to 98 parts by mass, more preferably 10 to 70 parts by mass, and even more preferably 20 to 60 parts by mass, particularly preferably 30 to 50 parts by mass. By setting the content of component (A) within the aforementioned range, the refractive index can be reduced and the adhesion improved.

[0150] (B) Polymerization initiator

[0151] The resin composition of this embodiment contains (B) a polymerization initiator (hereinafter also referred to as "(B) component").

[0152] (B) is not particularly limited if it can initiate the polymerization reaction of (A1) and (A2).

[0153] In this embodiment, component (B) can be made by using appropriate compounds based on the types of reactive functional groups possessed by components (A1) and (A2).

[0154] As component (B), it can be used alone or in combination with two or more.

[0155] As component (B) of this embodiment, a photopolymerization initiator is preferably used.

[0156] There are no particular limitations on whether a photopolymerization initiator is a compound such as an acid, base, or free radical that produces (A1) component and (A2) by irradiating an active energy line.

[0157] Here, active energy lines include all light in a broad sense, such as alpha rays, beta rays, electromagnetic waves such as gamma rays and X-rays, electron beams (EB), ultraviolet light of about 100 nm to 400 nm, and visible light of about 400 nm to 800 nm, with ultraviolet light being the preferred option.

[0158] When the reactive functional groups of components (A1) and (A2) are cationic polymerizable groups, a photoacid generator is preferably used as a photopolymerization initiator.

[0159] Photoacid generators are compounds that produce acids by irradiating active energy lines.

[0160] Cationic polymerization occurs between the cationic polymerizable groups of components (A1) and (A2) through the catalytic effect of the acid generated by the self-photogenic acid generator.

[0161] There are no particular limitations on photoacid generators. Examples include: onium salts, halogenated compounds, diazomethane compounds, sulfone compounds, sulfonic acid compounds, and other compounds that produce acids through radiation.

[0162] From the viewpoint of having a low refractive index and high transparency, onium salts are preferred as photoacid generators. Onium salts are salt compounds of onium ions and anions. Onium salts undergo photoreactions to release Lewis acids or Brinzyl acids (protic acids).

[0163] There is no particular limitation on the onium salt, but it is preferably selected from at least one onium salt selected from the group consisting of onium borate salt and onium gallate salt.

[0164] In this case, the onium salt is preferably composed of at least one cation selected from the group consisting of monium and matte.

[0165] There are no particular limitations on gallic acid onium salts, and onium salts represented by the following general formula (3) can be used.

[0166] [Chemistry 3]

[0167] In equation (3), R 13 ~R 16 R represents an alkyl, aryl, or heterocyclic group having 1 to 18 carbon atoms, respectively. 13 ~R 16 At least one of them is an aryl group, and the number of carbons in the aryl group (excluding the number of carbons in the substituents) is 6 to 14. The aryl group may have substituents. E represents elements in groups 15-17 (as designated by the International Union of Pure and Applied Chemistry, IUPAC) with a valence n. n is an integer from 1 to 3. R 17 As an organic group bonded to E, R 17 The number of R is n+1, and there are (n+1) R 17 They can be the same or different from each other, and there are two or more R's.17 They can form ring structures containing element E directly or via -O-, -S-, -SO-, -SO2-, -NH-, -CO-, -COO-, -CONH-, alkylene, or phenylene. Gallic onium salts may contain an anion having a tetraphenyl gallate skeleton, wherein the hydrogen atom of the phenyl group of the tetraphenyl gallate skeleton may be substituted with at least one halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine atoms.

[0168] The anion with a tetraphenylgallate skeleton can be tetra(pentafluorophenyl)gallate.

[0169] Gallic acid onium salts can be synthesized, for example, based on the method described in Japanese Patent Application Publication No. 2017-048325.

[0170] Examples of gallic acid onium salts include tetra(pentafluorophenyl)gallic acid 4-isopropyl-4'-methyldiphenyl sulfonium, tetra(pentafluorophenyl)gallic acid-triarylsulfonium, tetra(pentafluorophenyl)gallic acid diphenyl[4-(phenylthio)phenyl]sulfonium, and tetra(pentafluorophenyl)gallic acid 4-isopropylphenyl(p-tolyl)sulfonium, but are not limited to these compounds.

[0171] There are no particular limitations on the borate salts, and the onion salts represented by the following general formula (4) can be used.

[0172] [Chemistry 4]

[0173] In general formula (4), R 18 ~R 21 Each is independently an alkyl group having 1 to 18 carbon atoms or Ar, wherein at least one is Ar, and Ar is an aryl group having 6 to 14 carbon atoms (excluding the carbon number of the following substituents), and a portion of the hydrogen atoms in the aryl group may be derived from an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 8 carbon atoms substituted with a halogen atom, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, or -OR. 23 The alkoxy or aryloxy group represented by R 24 CO- represents the acyl group, R 25 COO- represents the acyloxy group, -SR 26 The alkylthio or arylthio group, -NR 27 R 28 The substitution of amino or halogen atoms is represented. R 23 ~R 26 It is an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms. R 27 and R28 It consists of hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, or aryl groups having 6 to 14 carbon atoms; E represents elements in groups 15 to 17 (IUPAC notation) with an atomic valence n. n is an integer from 1 to 3. R 22 As an organic group bonded to E, R 22 The number of R is n+1, and there are (n+1) R 22 They can be the same or different from each other, and there are two or more R's. 22 They can form ring structures containing element E directly or via -O-, -S-, -SO-, -SO2-, -NH-, -CO-, -COO-, -CONH-, alkylene, or phenylene. Onium borate salts may contain anion having a tetraphenylborate skeleton, wherein the hydrogen atom of the phenyl group in the tetraphenylborate skeleton may be substituted with at least one halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine atoms.

[0174] The anion with a tetraphenylborate skeleton can be tetra(pentafluorophenyl)borate.

[0175] Onium borate salts can be synthesized, for example, based on the method described in Japanese Patent Application Publication No. 2014-205624.

[0176] Specific examples of onium borate salts include tetra(pentafluorophenyl)boronic acid 4-isopropyl-4'-methyldiphenyl sulfonium tetra(pentafluorophenyl)boronic acid-triarylsulfonium tetra(pentafluorophenyl)boronic acid diphenyl[4-(phenylthio)phenyl]sulfonium tetra(pentafluorophenyl)boronic acid 4-isopropylphenyl(p-tolyl)sulfonium tetra(pentafluorophenyl)boronic acid, but are not limited to these compounds.

[0177] (B) The content of component (B) in the resin composition is not particularly limited. From the viewpoint of polymerizability or the viewpoint of making the cured product low in refractive index and high in transparency, it is 0.05 to 20.0 parts by mass relative to 100 parts by mass of the siloxane compound having reactive functional groups in (A), preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass.

[0178] Furthermore, the content of component (B) can be appropriately designed based on various factors such as the type or properties of the polymerizable compound, the type and amount of irradiation of the active energy line (in the case of using an active energy line), heating temperature, curing time, humidity, and the thickness of the resin composition, and is not limited to the range described above.

[0179] [Any other ingredients]

[0180] The resin composition of this embodiment may, as needed, contain any component other than the components (A1), (A2), and (B), such as those described below, without prejudice to the spirit of this embodiment.

[0181] (C) Inorganic fillers

[0182] The resin composition of this embodiment may contain (C) inorganic filler (hereinafter also referred to as "(C) component") as any component.

[0183] (C) If the component is a granular body formed from inorganic materials, there are no particular limitations.

[0184] As inorganic materials, silicon dioxide, talc, aluminum oxide, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, calcium sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, boron nitride, etc. can be used.

[0185] (C) Components may be used alone or in combination with two or more.

[0186] As for component (C), from the viewpoint of refractive index, it is preferable to use silicon dioxide particles.

[0187] In addition, silicon dioxide is preferably amorphous silicon dioxide.

[0188] Regarding component (C), from the perspective of preventing aggregation, its surface can be treated with coupling agents such as silane coupling agents.

[0189] (C) The shape of the component is not particularly limited and can be any of the following: spherical, flake-like, needle-like, or amorphous.

[0190] In resin compositions using flake-like or needle-like inorganic fillers as optical adhesives, light may sometimes scatter if the orientation of the inorganic fillers is disordered. Therefore, from the viewpoint of refractive index or transmittance, silica particles are preferably spherical, with a sphericity of 0.8 or higher, and more preferably approximately spherical with a sphericity of 0.9 or higher.

[0191] (C) The average particle size of the component is preferably 5.0 μm or less, more preferably 3.0 μm or less, even more preferably 1.0 μm or less, and particularly preferably 0.5 μm or less.

[0192] In this specification, the term "average particle size" unless otherwise specified refers to the median particle size (D50) of the volume standard determined by laser diffraction scattering method in accordance with International Standardization Organization (ISO) 13320 (2020).

[0193] Transmittance can be improved by setting the average particle size of component (C) below the upper limit.

[0194] (C) There is no particular limitation on the lower limit of the average particle size of the component, but from the viewpoint of the viscosity of the resin composition, it is preferably 0.1 μm or more, and more preferably 0.2 μm or more.

[0195] (C) The average particle size of the component is preferably 0.1 μm to 5.0 μm, more preferably 0.2 μm to 2.0 μm.

[0196] Inorganic fillers with different average particle sizes can be used in combination. For example, inorganic fillers with an average particle size of 0.1 μm or more but less than 0.5 μm can be used in combination with inorganic fillers with an average particle size of 0.5 μm to 5.0 μm.

[0197] Furthermore, when using silica as an inorganic filler, its manufacturing method is not particularly limited. Examples include: spherical silica powder obtained by reacting metallic silicon with oxygen; spherical silica powder obtained by melting pulverized silica; and silica fillers obtained by sol-gel method, sedimentation method, or aqueous solution wet method. Among these, from the viewpoint of optical properties, silica particles obtained by the sol-gel method, i.e., sol-gel silica particles, are particularly preferred as they have high sphericity and a relatively sharp particle size distribution.

[0198] When the total amount of the resin composition is set to 100 parts by mass, the content of component (C) in the resin composition of this embodiment is preferably 0.1 parts by mass to 80 parts by mass, more preferably 5 parts by mass to 70 parts by mass, and even more preferably 10 parts by mass to 60 parts by mass.

[0199] By setting the content of component (C) within the range described above, reflow resistance is improved and the refractive index is reduced.

[0200] (D) Oxycyclic butane compounds

[0201] The resin composition of this embodiment may contain (D)oxetane compounds (hereinafter also referred to as "(D) components") as any component.

[0202] (D) If the component is a compound containing an oxobutane ring, there are no special restrictions.

[0203] By including component (D) in the resin composition, the initial adhesion can be improved. Preferably, it does not contain compounds such as oxobutane compounds having aromatic rings, which may increase the refractive index of the resin composition.

[0204] (D) There is no particular limitation on the mixing ratio of the components. When the total amount of the resin composition is set to 100 parts by mass, it is preferably 1 to 5 parts by mass.

[0205] Examples of oxetane compounds include 3,3'-(oxybis(methylene)bis(3-ethyloxetane), 3-ethyl-3-hydroxymethyloxetane, 3-(methyl)allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetane-butylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxetane-butylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxetane-butylmethoxy)ethyl]phenyl ether, isobutoxymethyl (3-ethyl-3-oxetane-butylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetane-butylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetane-butylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetane-butylmethyl) ether, and tetrabromophenyl (3-ethyl-3-oxetane-butylmethyl) The ethers include, but are not limited to, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetane butylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetane butylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetane butylmethyl) ether, ethylene glycol bis(3-ethyl-3-oxetane butylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetane butylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetane butylmethyl) ether, trimethylolpropane tri(3-ethyl-3-oxetane butylmethyl) ether, pentaerythritol tri(3-ethyl-3-oxetane butylmethyl) ether, pentaerythritol tetra(3-ethyl-3-oxetane butylmethyl) ether, dipentaerythritol tetra(3-ethyl-3-oxetane butylmethyl) ether, and di-trimethylolpropane tetra(3-ethyl-3-oxetane butylmethyl) ether.

[0206] Commercially available products as oxetane compounds include, for example: OXT-212, OX-221, OXT-213, OXT-101 (manufactured by Dong-A Synthetic Co., Ltd.).

[0207] (E) Other additives

[0208] The resin composition of this embodiment may, as needed and without prejudice to the spirit of this embodiment, also contain other additives, such as coupling agents, stabilizers, ion traps, leveling agents, antioxidants, defoamers, viscosity modifiers, solvents, etc.

[0209] The content of each additive can be appropriately selected.

[0210] There is no particular limitation on the method for manufacturing the resin composition of this embodiment. For example, the resin composition of this embodiment can be obtained by simultaneously or separately introducing component (A), component (B), and, if necessary, component (C), component (D), and other additives (E) into a suitable mixer, heating them as needed to melt them, and simultaneously stirring and mixing them to form a homogeneous composition.

[0211] The mixer is not particularly limited and can include a pulverizer, Henschel mixer, three-roll mill, ball mill, planetary mixer, and bead mill, among others, which include a stirring device and a heating device. Additionally, these devices can be used in combination.

[0212] The resin composition thus obtained has both photocurability and thermocurability.

[0213] [Viscosity of the resin composition]

[0214] The viscosity of the resin composition in this embodiment is not particularly limited, but can be adjusted appropriately according to the application.

[0215] For example, as long as the components are selected and the mixing ratio is appropriately adjusted so that the viscosity of the resin composition at 25°C is in the range of 0.01 Pa·s to 1,000 Pa·s.

[0216] In this manual, unless otherwise specified, viscosity is expressed using values ​​measured according to Japanese Industrial Standard JIS K6833. Specifically, it can be determined using a Type E viscometer at a rotation speed of 10 rpm. There are no particular limitations on the machine, rotor, or measurement range used.

[0217] From the viewpoint of achieving good injectability, the viscosity of the resin composition at 25°C can be 0.05 Pa·s to 200 Pa·s, preferably 0.1 Pa·s to 100 Pa·s, more preferably 0.1 Pa·s to 50 Pa·s, and even more preferably 0.1 Pa·s to 20 Pa·s.

[0218] If the viscosity of the resin composition is too low, it will fail to maintain its shape and flow during application. If the viscosity of the resin composition is too high, it will result in poor injectability or unevenness during application.

[0219] In addition, the thixotropic index (TI) value of the resin composition is preferably 0.5 to 3.0.

[0220] In this specification, TI is the ratio of viscosity at 5 rpm to viscosity at 50 rpm, measured using an E-type viscometer at 25°C, and is calculated by dividing the viscosity at 5 rpm by the viscosity at 50 rpm.

[0221] The Thixotropic viscosity (TI) value is an indicator of the dependence of viscosity on shear rate (the rotational speed of a viscometer) and represents thixotropy. For example, the TI value of a Newtonian fluid like water, whose viscosity does not change even when the shear rate changes, is 1. When the TI value is less than 1, lower shear force indicates lower viscosity compared to higher shear force; conversely, when the TI value is greater than 1, lower shear force indicates higher viscosity compared to higher shear force. A higher TI value indicates greater thixotropy.

[0222] If the TI value is 0.5 to 3.0, the workability of the resin composition becomes good when injected. The resin composition can have thixotropy close to that of a Newtonian fluid with a TI value of 0.8 to 1.2, or it can have thixotropy of a non-Newtonian fluid with a thixotropic index greater than 1.2.

[0223] [Curing of the resin composition]

[0224] The resin composition of this embodiment can be easily cured by irradiation with the active energy line, preferably light with a wavelength of 10 nm to 600 nm, more preferably ultraviolet light with a wavelength of 100 nm to 500 nm, further preferably ultraviolet light with a wavelength of 250 nm to 450 nm, and particularly preferably ultraviolet light with a wavelength of 300 nm to 400 nm, thereby producing a cured product.

[0225] When the resin composition of this embodiment is cured by ultraviolet irradiation, the amount of ultraviolet irradiation (cumulative light intensity) used is preferably 500 mJ / cm. 2 ~30,000 mJ / cm 2 There are no particular limitations on the devices used for irradiating ultraviolet light; for example, previously known devices can be cited.

[0226] [Refractive index, transmittance, and reflow resistance of the hardened material]

[0227] The resin composition of this embodiment, by having a cyclic siloxane compound containing (A1) a reactive functional group and a linear siloxane compound containing (A2) a reactive functional group as (A) siloxane compound, exhibits excellent optical properties or heat resistance when the cured material is formed.

[0228] Specifically, the cured resin composition of this embodiment has a low refractive index, high transparency, and good reflow resistance.

[0229] The hardened material of this embodiment has a refractive index of 1.47 or less at a wavelength of 1310 nm and / or 589 nm and at 25°C, preferably 1.46 or less, more preferably 1.45 or less, and even more preferably 1.44 or less.

[0230] The refractive index of the hardened material at a wavelength of 1310 nm and / or 589 nm and at 25°C can be 1.40 or more but less than 1.47, preferably 1.41 or more but less than 1.47, more preferably 1.42 to 1.46, and even more preferably 1.43 to 1.46.

[0231] Unless otherwise specified, the refractive index in this specification is expressed using the value determined in accordance with the JIS K7142:2014A method.

[0232] The hardened material of this embodiment has a transmittance of 80% or more at a thickness of 100 μm, a wavelength of 1310 nm and / or 589 nm, and a temperature of 25°C, preferably 85% or more, more preferably 90% or more, and even more preferably 92% or more.

[0233] The transmittance of the hardened material at a thickness of 100 μm, a wavelength of 1310 nm and / or 589 nm, and a temperature of 25°C can be in the range of 80% to 99%, preferably 85% to 95%, more preferably 87% to 95%, and even more preferably 90% to 95%.

[0234] Unless otherwise specified, the transmittance in this specification is expressed using the value measured in accordance with JIS K7105.

[0235] The cured resin composition of this embodiment exhibits excellent heat resistance, with particularly excellent reflow resistance.

[0236] In this specification, reflow resistance refers to the property of withstanding thermal shock at a maximum temperature of 260°C for 1 minute. That is, the cured resin composition of this embodiment has the following property: when encapsulating electronic components, the change in physical properties is small before and after the reflow process (maximum temperature of about 260°C) for soldering.

[0237] For example, the resin composition of this embodiment has the property that when a cured material is formed, the change in adhesion strength is small before and after the reflow process.

[0238] The reflow resistance of the cured resin composition can be evaluated by assessing the rate of reduction in adhesive strength.

[0239] Regarding the adhesion strength of the hardened material, there are no particular limitations if the same method is used before and after the reflow process; for example, a bare film shear test can be performed to determine it.

[0240] The method for determining the shear strength of bare wafers is as follows.

[0241] (1) The resin composition (sample) is coated on a glass substrate.

[0242] (2) The Si chip is placed on the coated sample to make a test piece.

[0243] (3) The test piece is hardened by ultraviolet (UV) irradiation from the glass substrate side.

[0244] (4) After the sample has been light-cured, the shear strength of the bare sheet should be determined quickly using an adhesive strength tester. The value should be set as the adhesive strength before reflow.

[0245] (5) Next, the test piece was subjected to a heat treatment for 6 minutes. For the heat treatment, the temperature was increased from room temperature, and each of the following six stages—170°C, 160°C, 160°C, 260°C, 255°C, and cooling—was performed for 1 minute, constituting one group. This heat treatment was repeated for 3 groups. After the heat treatment, the shear strength of the bare sheet was quickly measured in the same manner as before reflow. This value was taken as the adhesion strength after reflow.

[0246] (6) Calculate the rate of decrease in adhesion strength before and after the reflow process according to the following formula (1).

[0247] [Formula 2]

[0248] The heat treatment described in (5) is a heat treatment that mimics the reflow process performed in the packaging process. The sample before heat treatment is referred to as "before reflow process", and the sample after heat treatment is referred to as "after reflow process".

[0249] Furthermore, the smaller the absolute value of the rate of decrease in adhesion strength before and after the reflow process as expressed in Equation (1), the smaller the change caused by heat treatment, and therefore it is preferred.

[0250] Regarding the cured resin composition of this embodiment, the absolute value of the rate of decrease in adhesion strength before and after the reflow process, as expressed in formula (1), can be 74% or less, preferably 65% ​​or less, more preferably 55% or less, and even more preferably 50% or less, particularly preferably 40% or less. Furthermore, there is no particular limitation on the lower limit of the absolute value of the rate of decrease in adhesion strength, for example, it can be 0% or more.

[0251] [Uses of the resin composition]

[0252] The resin composition of this embodiment has excellent optical properties or heat resistance, and therefore can be used for a variety of applications.

[0253] For example, the resin composition of this embodiment can be used as an adhesive or sealant, or a raw material thereof, for fixing, joining or protecting optical components, electronic components or semiconductor components.

[0254] Preferably, the resin composition of this embodiment is used as an adhesive composition.

[0255] [Adhesive Composition]

[0256] The adhesive composition of this embodiment comprises the resin composition and can be used as an adhesive for joining parts together.

[0257] There are no particular limitations on the parts to which the adhesive composition of this embodiment is applied, but it is preferable to use the adhesive composition of this embodiment to bond optical parts.

[0258] As optical components, examples include optical fibers, fiber arrays, optical waveguide elements, lenses, filters, diffraction gratings, and active optical elements, but are not limited to these.

[0259] Furthermore, the adhesive composition of this embodiment has excellent optical properties or heat resistance, and is therefore particularly preferred for use as an optical adhesive for silicon photonics.

[0260] Furthermore, it is preferable to use the adhesive composition of this embodiment for bonding optical fibers and optical waveguide elements.

[0261] As described below, the adhesive composition of this embodiment can be used to fix the optical fiber 10 in the groove (V groove 33) formed in the optical waveguide element 30, or to couple the optical fiber 10 to the optical waveguide 32 of the optical waveguide element 30.

[0262] In addition, it is preferable to use the adhesive composition of this embodiment to simultaneously fix the optical fiber 10 in the groove, i.e., the V-groove 33, formed in the optical waveguide element 30 and to couple the optical fiber 10 to the optical waveguide 32 of the optical waveguide element 30.

[0263] For example, the adhesive composition of this embodiment can be used in methods for fixing optical fibers in grooves formed in optical waveguide elements, and in methods for optically coupling optical fibers to optical waveguide elements.

[0264] In addition, the adhesive composition of this embodiment can also be used to simultaneously perform a method of fixing an optical fiber in a groove formed in an optical waveguide element and optically coupling the optical fiber to the optical waveguide element.

[0265] [Fiber optic array]

[0266] Preferably, the adhesive composition (resin composition) of this embodiment is used for bonding optical fibers and optical waveguide elements.

[0267] Specifically, it is suitable to use the adhesive composition (resin composition) of this embodiment to construct the optical fiber array 1.

[0268] like Figures 1-4 As shown, the fiber array 1 of this embodiment includes an optical fiber 10 and an adhesive layer 20. Furthermore, the optical fiber 10 is covered by a cladding layer 11 and is shown in a configuration with an optical fiber 12. In the fiber array 1, the optical fiber 10 is optically coupled to the optical waveguide 32 of the optical waveguide element 30 via the adhesive layer 20.

[0269] like Figures 1-4 As shown, the fiber array 1 of this embodiment has a substrate 31 with a groove, namely a V-groove 33, formed to accommodate the optical fiber 10, and a pressure plate 40 that is then fixed to the surface of the optical fiber 10. The optical fiber 10 is then fixed in the V-groove 33 by an adhesive layer 20. Figure 3 , Figure 4 Furthermore, the adhesive layer 20 connects the optical fiber 10 to the optical waveguide element 30. Figure 3 And the substrate 31, in which the optical fiber 10 is housed in the V-groove 33, is connected to the pressure plate 40. Figure 4 ).

[0270] In addition, the substrate 31 may be made of glass, semiconductor, organic resin, etc., and preferably a semiconductor substrate.

[0271] Additionally, a ball grid array electrode (not shown) can be provided on one side of the substrate. By providing a ball grid array electrode on one side of the substrate, multiple electrical interfaces can be realized at high density, thus enabling miniaturization of silicon photonic devices. Furthermore, the ball grid array electrode is envisioned to be packaged and fixed to another substrate, etc., through a reflow process. Therefore, the adhesive layer in the fiber array of this embodiment is required to have heat resistance so as to withstand the temperature or time required for reflow heating.

[0272] The adhesive layer 20 can be formed using the adhesive composition (resin composition) of this embodiment.

[0273] That is, the fiber array 1 of this embodiment may include an optical fiber 10 and an adhesive layer 20. The optical fiber 10 is optically coupled to the optical waveguide element 30 through the adhesive layer 20. The adhesive layer 20 includes (A1) a cyclic siloxane compound with reactive functional groups, (A2) a linear siloxane compound with reactive functional groups, and (B) a polymerization initiator.

[0274] In other words, the fiber array 1 of this embodiment may include an adhesive composition (resin composition), an optical fiber 10, and an optical waveguide element 30. The adhesive composition (resin composition) includes (A1) a cyclic siloxane compound having reactive functional groups, (A2) a linear siloxane compound having reactive functional groups, and (B) a polymerization initiator. The optical fiber 10 is optically coupled to the optical waveguide element 30 through the adhesive composition (resin composition).

[0275] At this time, the fiber array 1 has a substrate 31 with a V-groove 33 for accommodating the fiber 10 and a pressure plate 40 fixed to the surface of the fiber 10. The fiber 10 is fixed in the V-groove 33 by an adhesive layer 20. The adhesive layer 20 connects the fiber 10 to the optical waveguide element 30 and connects the substrate 31 with the fiber 10 in the V-groove 33 to the pressure plate 40.

[0276] [Optical Waveguide Module]

[0277] Alternatively, the fiber array 1 of this embodiment can be used to construct the optical waveguide module 50 (optical waveguide device). Figure 1 ).

[0278] The optical waveguide module 50 of this embodiment includes the optical fiber array 1.

[0279] Specifically, the optical waveguide module 50 of this embodiment includes an optical fiber array 1, an adhesive layer 20, and an optical waveguide element 30. The optical fiber array 1 is optically coupled to the optical waveguide 32 of the optical waveguide element 30 through the adhesive layer 20.

[0280] The adhesive layer 20 can be formed using the adhesive composition (resin composition) of this embodiment.

[0281] Furthermore, there are no particular limitations on the optical waveguide element 30 in the fiber array 1 and optical waveguide module 50 of this embodiment if it is an element used in an optical integrated circuit.

[0282] The optical waveguide module 50 of this embodiment can be incorporated in the form of a silicon photonics device.

[0283] [Manufacturing methods for fiber optic arrays]

[0284] The fiber array 1 of this embodiment is manufactured by a method of manufacturing a fiber array 1 in which an optical fiber 10 is optically coupled to an optical waveguide element 30 through an adhesive layer 20. The adhesive layer 20 is formed from a cured adhesive composition (resin composition) comprising (A1) a cyclic siloxane compound having reactive functional groups, (A2) a linear siloxane compound having reactive functional groups, and (B) a polymerization initiator.

[0285] At this time, the steps of fixing the optical fiber 10 in the groove (V-groove 33) formed in the optical waveguide element 30 and coupling the optical fiber 10 to the optical waveguide 32 of the optical waveguide element 30 can be performed independently. Alternatively, in the manufacturing method of the fiber array 1 in this embodiment, the steps of fixing the optical fiber 10 in the groove (V-groove 33) formed in the optical waveguide element 30 and coupling the optical fiber 10 to the optical waveguide 32 of the optical waveguide element 30 can be performed simultaneously.

[0286] The following describes a method for fixing the optical fiber 10 to the optical waveguide element 30. Furthermore, this fixing method is merely an example, and this disclosure can be implemented in various modified and improved forms based on the knowledge of those skilled in the art.

[0287] First, the optical fiber 10 is inserted into the V-groove 33, so that the end of the optical fiber 10 abuts against the side of the optical waveguide 32. Here, proper alignment is performed to reduce losses at the connection between the optical fiber 10 and the optical waveguide 32.

[0288] Next, the pressure plate 40 is positioned on the optical fiber 10. Then, the adhesive composition (resin composition) is dropped into the V-groove 33. Alternatively, the pressure plate 40 may be integrally formed with the substrate 31.

[0289] The adhesive composition (resin composition) dropped into the V-groove 33 impregnates into the gap between the optical fiber 10 and the V-groove 33 through capillary action, and also impregnates along the abutment of the optical fiber 10 and the pressure plate 40, as well as into the gap between the optical fiber 10 and the optical waveguide 32. Therefore, the adhesive composition (resin composition) needs to be injectable in order to impregnate into both the gap between the optical fiber 10 and the V-groove 33 and the gap between the optical fiber 10 and the optical waveguide 32, and the viscosity or TI value of the adhesive composition (resin composition) needs to be set to an appropriate value.

[0290] Next, the adhesive composition (resin composition) is cured by irradiating it with ultraviolet light, thereby bonding the optical fiber 10 to the optical waveguide 32, the optical fiber 10 to the V-groove 33, and the optical fiber 10 to the pressure plate 40. Alternatively, a heat-based curing step can be added after the ultraviolet-based curing step.

[0291] That is, the adhesive layer 20 in this embodiment can also serve the following functions: to couple the optical fiber 10 to the optical waveguide 32 of the optical waveguide element 30, to fix the optical fiber 10 in the groove, i.e., the V-groove 33, formed in the optical waveguide element 30, and to fix the optical fiber 10 to the pressure plate 40.

[0292] That is, the adhesive layer 20 of this embodiment can be used for both optical path coupling and V-groove fixing.

[0293] In addition, the adhesive layer 20 may not necessarily perform these bonding simultaneously. It can also be used as an adhesive layer for optical path coupling of optical fiber 10 and optical waveguide 32 of optical waveguide element 30, or as an adhesive layer for fixing optical fiber 10 to V-groove 33 formed in the groove of optical waveguide element 30.

[0294] [method]

[0295] As shown in the examples described later, in the resin composition of this embodiment, the optical properties or heat resistance of the cured material are excellent when both (A) are cyclic siloxane compounds containing (A1) having reactive functional groups and linear siloxane compounds containing (A2) having reactive functional groups.

[0296] Therefore, this embodiment provides a method for reducing the refractive index of a cured resin composition (adhesive composition), which includes a step of combining (A1) a cyclic siloxane compound having reactive functional groups, (A2) a linear siloxane compound having reactive functional groups and (B) a polymerization initiator.

[0297] In addition, this embodiment provides a method for suppressing the reduction of adhesion strength of a cured resin composition (adhesive composition) caused by heating, which includes a step of combining (A1) a cyclic siloxane compound having reactive functional groups, (A2) a linear siloxane compound having reactive functional groups and (B) a polymerization initiator.

[0298] [Example]

[0299] The present invention will now be described in more detail through examples and comparative examples, but the present invention is not limited to these examples. Furthermore, in the following examples, unless otherwise specified, parts and % represent parts by mass and percentage by mass.

[0300] [Examples 1-13, Comparative Example 1, Comparative Example 2]

[0301] Resin compositions were prepared by mixing the specified amounts of each component using a three-roll mill according to the formulations shown in Tables 1 to 3. In Tables 1 to 3, the amount of each component is expressed in parts by mass (unit: g). The components used in the examples and comparative examples are as follows.

[0302] • (A1) Cyclic siloxane compounds ((A1) components)

[0303] (A1-1) KR-470 (manufactured by Shin-Etsu Chemical Co., Ltd., alicyclic epoxy group, epoxy functional group 4, viscosity at 25°C 3 Pa·s, epoxy equivalent 200 g / mol) represented by the following formula

[0304] [Chemistry 5]

[0305] (A1-2) A cyclic dimethylsiloxane compound in which n is 4 and has four 3-glycidoxypropyl groups in the molecule (product name: EP-3400L, manufactured by ADEKA, non-alicyclic epoxy group, epoxy functional group number 4, viscosity at 25°C 100 Pa·s, epoxy equivalent 174 g / mol)

[0306] (A1-3) X-40-2678 (manufactured by Shin-Etsu Chemical Co., Ltd., alicyclic epoxy group, epoxy functional group number 2, viscosity at 25°C 120 Pa·s, epoxy equivalent 290 g / mol) is represented by the following formula.

[0307] [Chemistry 6]

[0308] (A1-4) X-40-2728 (manufactured by Shin-Etsu Chemical Co., Ltd., non-alicyclic epoxy group, epoxy functional group number 2, viscosity at 25°C 26 mPa·s, epoxy equivalent 280 g / mol) represented by the following formula (R is alkyl)

[0309] [Chemistry 7]

[0310] • (A2) Straight-chain siloxane compounds ((A2) component)

[0311] (A2-1) The modified silicone oil with alicyclic epoxy groups at both ends represented by the following formula (product name: X-22-169AS, manufactured by Shin-Etsu Chemical Co., Ltd., alicyclic epoxy group, number average molecular weight 1,000, viscosity at 25°C 25 Pa·s, epoxy equivalent 500 g / mol).

[0312] [Chemistry 8]

[0313] (A2-2) The following formula (m=0, R) a =Methyl, R b = Organic groups with epoxy groups) refers to modified silicone oil with epoxy groups (glycidyl ether structure) at both ends (product name: KF-105, manufactured by Shin-Etsu Chemical Co., Ltd., non-alicyclic epoxy group, number average molecular weight 980, viscosity at 25°C 15 Pa·s, epoxy equivalent 490 g / mol).

[0314] [Chemistry 9]

[0315] • (B) Polymerization initiator ((B) component)

[0316] (B-1) 4-Isopropyl-4'-methyldiphenylboronic acid as a boronic acid salt

[0317] (B-2) Tetra(pentafluorophenyl)gallic acid 4-isopropyl-4'-methyldiphenyl monazine as an onium salt of gallic acid

[0318] • (C) Inorganic particles ((C) components)

[0319] (C-1) Spherical silica particles (Product name: KE-S30HG, manufactured by Japan Catalyst Co., Ltd., D50 is 0.3 μm, spherical sol-gel silica particles)

[0320] • (D) Oxybutane compounds ((D) components)

[0321] (D-1) 3,3'-(oxybis(methylene)bis(3-ethyloxetane) (Product name: OXT-221, manufactured by Toa Synthetic Co., Ltd.)

[0322] [Evaluation of characteristics]

[0323] In the examples and comparative examples, the viscosity of the resin composition and the properties of the cured product obtained by curing the resin composition were measured in the following manner (adhesion strength, strength reduction rate before and after reflow, refractive index, transmittance).

[0324] (Viscosity of the resin composition)

[0325] Using an E-type viscometer (model: TVE-22H, rotor name: 1°34'×R24) manufactured by Toki Sangyo Co., Ltd. (set to the appropriate measurement range (H, R or U)), the viscosity of the resin composition was measured within 1 hour after its preparation at 25°C and a rotor speed of 10 rpm. The value was read 1 minute after the start of the measurement.

[0326] (Curing of the resin composition)

[0327] The hardening conditions were set as follows: a UV irradiation machine using a metal halide lamp as the lamp source, with a peak wavelength of 365 nm and a heat output of 30,000 mJ / cm². 2 After irradiating with UV light, the accumulated light intensity is dried at 120°C for 60 minutes using a dryer.

[0328] (Refractive index)

[0329] The refractive index of a 100 μm thick cured film made from a resin composition was measured at 589 nm using an Abbe refractometer (manufactured by Atago Corporation, NAR-2T). Additionally, the refractive index of a cured resin composition formed on a glass substrate was measured at 1310 nm using a spectroscopic ellipsometry (manufactured by Semilab Corporation, SE-2000).

[0330] (Transmission rate)

[0331] The transmittance of a 100 μm thick cured material made from a resin composition was determined using a UV-Vis spectrophotometer (V-670, manufactured by Nippon Spectrophotometer Co., Ltd.) at measurement wavelengths of 589 nm and 1310 nm.

[0332] (Reflow resistance)

[0333] The adhesion strength of the cured resin composition was determined by bare sheet shear test.

[0334] The method for determining the shear strength of bare wafers is as follows.

[0335] (1) The prepared resin composition (sample) is coated onto a glass substrate in the form of an adhesive. The coating size is set to 1.5 mm in length × 1.5 mm in width × 0.5 mm in thickness.

[0336] (2) Place 2 mm 2 The Si chip is placed on the coated sample to make a test piece.

[0337] (3) The test piece is hardened by UV irradiation from the glass substrate side under the hardening conditions.

[0338] (4) After the sample has been light-cured, the shear strength of the bare sheet should be determined quickly using a universal adhesive strength tester (Dage, Series 4000). The value should be set as the adhesive strength before reflow.

[0339] (5) Next, the test piece was subjected to a heat treatment for 6 minutes. For the heat treatment, the temperature was increased from room temperature, and each of the following six stages—170°C, 160°C, 160°C, 260°C, 255°C, and cooling—was performed for 1 minute, constituting one group. This heat treatment was repeated for 3 groups. After the heat treatment, the shear strength of the bare sheet was quickly measured in the same manner as before reflow. This value was taken as the adhesion strength after reflow.

[0340] (6) Calculate the rate of decrease in adhesion strength before and after the reflow process according to the following formula (1).

[0341] [Formula 3]

[0342] [Table 1]

[0343] [Table 2]

[0344] [Table 3]

[0345] [result]

[0346] According to Tables 1 to 3, the resin composition containing (A1) a cyclic siloxane compound with reactive functional groups, (A2) a linear siloxane compound with reactive functional groups, and (B) a polymerization initiator has a low refractive index, can suppress the decrease in adhesion even at high temperatures, and has excellent heat resistance.

[0347] Specifically, in Examples 1 to 13, the refractive index at wavelengths of 1310 nm and 589 nm and at 25°C is 1.47 or lower, which is considered a low refractive index. The decrease in adhesion strength before and after the reflow process is less than 74%, and the adhesion strength after reflow is 3.1 N / mm. 2 It exhibits excellent reflow resistance.

[0348] In addition, it is known that the resin compositions of Examples 1 to 13 have low viscosity and therefore excellent injectability.

[0349] In addition, it is known that the resin compositions of Examples 1 to 13 have high transmittance and therefore excellent transparency.

[0350] A comparison of Examples 1 to 7 shows that the refractive index and reflow resistance can be adjusted by changing the mixing ratio of the (A1) cyclic siloxane compound and the (A2) linear siloxane compound. Increasing the proportion of the (A1) cyclic siloxane compound improves the reflow resistance, while increasing the proportion of the (A2) linear siloxane compound lowers the refractive index.

[0351] A comparison of Examples 1 to 3 and Examples 4 to 6 shows that if (D)oxobutane compounds are included, the adhesion strength before reflux is higher.

[0352] A comparison of Examples 5 and 8 through 10 shows that regardless of the type (type or number of functional groups) of the (A1) cyclic siloxane compound, the refractive index is low and the reflow resistance is excellent. Furthermore, a comparison of Examples 5 and 8 or Examples 9 and 10 shows that when the functional groups of the (A1) cyclic siloxane compound are alicyclic epoxy groups, the reflow resistance is superior compared to non-alicyclic epoxy groups. Additionally, a comparison of Examples 5 and 9 shows that when the number of functional groups in the (A1) cyclic siloxane compound is high, the reflow resistance is excellent.

[0353] A comparison of Examples 5 and 11 shows that regardless of the type (functional group) of the (A2) linear siloxane compound, the refractive index is low and the reflow resistance is excellent. Furthermore, a comparison of Examples 5 and 11 shows that when the functional group of the (A2) linear siloxane compound is an alicyclic epoxy group, the reflow resistance is superior compared to the non-alicyclic epoxy group case.

[0354] As can be seen from Example 12, even without the presence of (C) inorganic filler, the refractive index is low and the reflow resistance is excellent.

[0355] Based on the comparison of Examples 4 and 13, it can be seen that regardless of the type of polymerization initiator (B), the refractive index is low and the reflow resistance is excellent.

[0356] Comparative Examples 1 and 2 are examples that do not contain either (A1) a cyclic siloxane compound having a reactive functional group or (A2) a linear siloxane compound having a reactive functional group.

[0357] In Comparative Example 1, which does not contain (A1) cyclic siloxane compounds, the reflow resistance is poor.

[0358] In Comparative Example 2, which does not contain (A2) linear siloxane compounds, the refractive index is high, the reflow resistance is poor, the viscosity is high, and the injection performance is poor.

[0359] [Industry availability]

[0360] The resin composition of the present invention has a low refractive index and good heat resistance, such as reflow resistance, making it effective as an adhesive, and particularly effective as an adhesive for optical components. Furthermore, the resin composition of the present invention does not contain fluorine compounds and can be made with a low refractive index, thus also being effective as an optical adhesive from an environmental point of view.

[0361] Explanation of icon numbers

[0362] 1: Fiber optic array

[0363] 10: Fiber optic

[0364] 11: Covering layer

[0365] 12: With fiber optic cable

[0366] 20: Adhesive layer

[0367] 30: Optical waveguide components

[0368] 31: Substrate

[0369] 32: Optical waveguide

[0370] 33: V-groove (groove section)

[0371] 40: Pressure plate

[0372] 50: Optical waveguide module (optical waveguide device)

Claims

1. A resin composition comprising: (A1) Cyclic siloxane compounds with reactive functional groups, (A2) Straight-chain siloxane compounds with reactive functional groups, and (B) Polymerization initiator.

2. The resin composition according to claim 1, wherein, The (A1) cyclic siloxane compound having reactive functional groups has two or more of the reactive functional groups.

3. The resin composition according to claim 1 or 2, wherein, The (A1) cyclic siloxane compound having reactive functional groups has cationic polymerizable groups.

4. The resin composition according to any one of claims 1 to 3, wherein, The (A1) cyclic siloxane compound with reactive functional groups is an epoxy-modified cyclic siloxane compound having two or four epoxy groups.

5. The resin composition according to any one of claims 1 to 4, wherein, The (A2) linear siloxane compound having reactive functional groups has one or more cationic polymerizable groups within its molecule.

6. The resin composition according to any one of claims 1 to 5, wherein, The (A2) linear siloxane compound with reactive functional groups has glycidyl ether structures at both ends.

7. The resin composition according to any one of claims 1 to 6, wherein, The mass ratio of the cyclic siloxane compound (A1) with reactive functional groups to the linear siloxane compound (A2) with reactive functional groups is 95:5 to 1:

99.

8. The resin composition according to any one of claims 1 to 7, further comprising (C) an inorganic filler.

9. The resin composition according to claim 8, wherein, When the total amount of the resin composition is set to 100 parts by mass, the content of the inorganic filler (C) is 0.1 parts by mass to 80 parts by mass.

10. The resin composition according to claim 8 or 9, wherein, The average particle size of the inorganic filler (C) is 0.1 μm to 5.0 μm.

11. The resin composition according to any one of claims 1 to 10, further comprising (D) oxetane compound.

12. A cured product, which is a cured product of the resin composition according to any one of claims 1 to 11.

13. The hardened material according to claim 12, wherein the refractive index at a wavelength of 1310 nm is less than 1.

47.

14. The hardened material according to claim 12 or 13, wherein, The hardened material has a transmittance of over 90% at a thickness of 100 μm and a wavelength of 1310 nm.

15. The hardened material according to any one of claims 12 to 14, wherein, The rate of decrease in adhesion strength before and after the reflow process, as expressed by the following formula (1), is less than 74%; [Formula 1] 。 16. An adhesive composition comprising the resin composition according to any one of claims 1 to 11, and Used for joining optical components.

17. The adhesive composition according to claim 16, used for securing an optical fiber in a groove formed in an optical waveguide element.

18. The adhesive composition according to claim 16 or 17, used for optical path coupling of optical fiber to optical waveguide element.

19. The adhesive composition according to any one of claims 16 to 18, used for simultaneously fixing an optical fiber in a groove formed in an optical waveguide element and optically coupling the optical fiber to the optical waveguide element.

20. An optical fiber array, comprising: The adhesive composition according to any one of claims 16 to 19 Fiber optics, and Optical waveguide components, The optical fiber is optically coupled to the optical waveguide element via the adhesive composition.

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