JP7426154B2 - resin composition - Google Patents

Description

The present invention relates to a resin composition, and particularly to a resin composition suitable for an adhesive for electronic parts.

When manufacturing image sensor modules used as camera modules for mobile phones and smartphones, one-component adhesives that harden at as low a temperature as possible are used. When manufacturing electronic components such as semiconductor devices, integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, and capacitors, it is preferable to use a one-component adhesive that hardens at as low a temperature as possible. In order to avoid deterioration of properties of peripheral members due to heat, and furthermore to improve manufacturing efficiency, a one-component adhesive that can be cured at lower temperatures is required.

Another important property required for a one-component adhesive used in the manufacture of image sensor modules and other electronic components is that it contains few components that evaporate during use (application) or curing.
If there are many components in the adhesive that evaporate when used at room temperature or when cured, especially when used for electronic components such as cameras and sensor modules, the volatiles may adhere to sensors, lenses, electrodes, etc. May cause contamination of them. In the module manufacturing process, cleaning with a solvent is generally performed in order to remove deposits that are generated during the process and cause such contamination. If the deposit is in liquid form, it can be removed relatively easily by such cleaning, but if the deposit is a solid substance that has hardened on the component, it becomes difficult to remove it from the component, resulting in a decrease in yield. There is a growing concern that manufacturing costs will increase. Furthermore, if bubbles are generated in the cured product due to volatile matter, the adhesive strength may decrease due to a decrease in bulk strength or a decrease in the interfacial area of the adherend. If bubbles are generated during curing, there is a concern that reliability may be lowered, such as the positional accuracy of the adherend being lowered due to deformation. Furthermore, if the volatile components are large, there are concerns about the impact on the health of workers, such as irritation to the eyes and bronchial tubes, which may lead to a deterioration of the working environment.

Traditionally, one-component adhesives for use in electronic components such as image sensor modules include thiol-based adhesives containing epoxy resins, polyfunctional thiol compounds, and curing accelerators as essential components, as well as radical initiators and anionic initiators. There are known acrylate resin adhesives that contain a binder as an essential component, and some that can be cured at about 80°C are also known. However, in order to improve manufacturing efficiency, there is a demand for one-component adhesives that can be cured at lower temperatures.

Patent Document 1 discloses a polymerization system containing diethylmethylene malonate monomer (DEMM) and a polymerization activator supported in an inert association, which can be cured in a short time even at low temperatures such as room temperature. .

Special Publication No. 2015-512460

However, the polymerization system of Patent Document 1 has many components that volatilize when used at room temperature or during curing, and when used for electronic components such as image sensor modules, there is a risk of adhesion and contamination to sensors, lenses, electrodes, etc. There is a concern that this will cause the above-mentioned problems such as deterioration of the working environment and decrease in reliability. On the other hand, in this polymerization system, when a monomer such as methylene malonate with a large molecular weight that is less volatile is used instead of diethyl methylene malonate monomer, the reaction initiation is delayed due to steric hindrance, resulting in curing at low temperature and in a short time. It may not be suitable for your purpose.

Furthermore, in recent years, plastic materials have been frequently used in electronic components. Plastic materials generally undergo greater deformation due to heat than inorganic materials such as metals and ceramics. In the manufacture of electronic parts, dimensional accuracy is an important issue that affects the characteristics of electronic parts, so adhesives used in the manufacture of electronic parts (especially those containing parts made of plastic materials) include: It is required that it can be cured at low temperatures. Furthermore, when manufacturing electronic components, if bonding can be performed at a temperature close to room temperature, the time and energy needed to change the temperature of the component or its surrounding environment can be reduced, which improves manufacturing efficiency. From this point of view, the curing temperature of adhesives used for manufacturing electronic components is preferably 80°C or lower, more preferably room temperature to 60°C.
Furthermore, shortening the time (gel time) required for the applied liquid adhesive to lose fluidity due to a curing reaction and become capable of fixing the adherend is extremely effective in improving manufacturing efficiency. Generally, lowering the curing temperature will reduce the speed of the curing reaction, but considering production efficiency, the gel time is preferably within 24 hours, more preferably within 12 hours, and within 6 hours. It is more preferably within 2 hours (120 minutes), and particularly preferably within 2 hours (120 minutes).
However, it has been difficult in the past to obtain a one-component adhesive that contains few volatile components and can be cured at low temperatures and in a short time as described above.

In order to solve the problems of the prior art described above, the present invention provides an image sensor module, etc. that can be cured in a relatively short time (within a few hours) at a low temperature around room temperature, and that is less likely to cause contamination of the surrounding area due to resin volatilization. The purpose of the present invention is to provide a resin composition suitable as a one-component adhesive for use in manufacturing electronic components.

The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result, have arrived at the present invention.

That is, the present invention includes, but is not limited to, the following inventions.

で表される構造単位を少なくとも１つ有し、かつ分子量が１８０～１００００である、２－メチレン－１，３－ジカルボニル化合物
（ｂ）少なくとも一種の第三級アミン化合物であって、各々、式［ＮＲ（ＣＨ_３）］_ｎ－Ｒ’（式中、各々のＲは独立に１価の炭化水素基を表し、ｎは１以上の整数であり、Ｒ’はｎ価の有機基を表す）で表され、分子量が１００～１０００であり、かつ式中の二置換アミノ基ＮＲ（ＣＨ_３）－の少なくとも１つについて、ｐＫａが８．０以上である、第三級アミン化合物 1. A resin composition containing the following components (a) and (b).
(a) at least one 2-methylene-1,3-dicarbonyl compound, each of the following formula (I):

2-methylene-1,3-dicarbonyl compound (b) having at least one structural unit represented by the following and having a molecular weight of 180 to 10,000; (b) at least one tertiary amine compound; Formula [NR(CH ₃ )] _n -R' (wherein each R independently represents a monovalent hydrocarbon group, n is an integer of 1 or more, and R' represents an n-valent organic group) ), has a molecular weight of 100 to 1000, and has a pKa of 8.0 or more for at least one of the disubstituted amino groups NR(CH ₃ )- in the formula.

2. 2. The composition according to item 1, wherein R is a methyl group in at least one of the disubstituted amino groups, and the pKa is 8.5 or more.

3. 2. The composition according to item 1, wherein R is a non-methyl hydrocarbon group in at least one of the disubstituted amino groups and has a pKa of 9.0 or more.

4. 2. The composition according to item 1, wherein n in the tertiary amine compound is 1.

5. 5. The composition according to any one of items 1 to 4 above, wherein the tertiary amine compound does not have an active hydrogen atom.

6. 6. The composition according to any one of the preceding items 1 to 5, wherein the tertiary amine compound is liquid at 80°C.

7. 7. The composition according to any one of the preceding items 1 to 6, wherein the tertiary amine compound is liquid at 25°C.

8. 8. The composition according to any one of the preceding items 1 to 7, wherein the amount of the tertiary amine compound is 0.01 to 30 mol% based on the 2-methylene-1,3-dicarbonyl compound.

9. 9. The composition according to any one of the preceding items 1 to 8, which is used for manufacturing electronic components.

10. An adhesive or a sealing material comprising the resin composition according to any one of items 1 to 9 above.

11. The adhesive or sealing material according to the preceding clause 10, which is for electronic components.

12. A film or prepreg comprising the resin composition according to any one of items 1 to 9 above.

13. The film or prepreg according to item 12 above, which is used for electronic components.

14. A semiconductor device comprising a cured product of the resin composition according to any one of items 1 to 9 above.

The resin composition of the present invention can be cured in a relatively short time (within several hours) even at low temperatures around room temperature, and is less likely to cause contamination of the surrounding area by the volatilized resin. It is suitable for use as a one-component adhesive. These characteristics make it possible to increase the manufacturing efficiency of electronic components, reduce contamination of the surrounding area during use and curing, maintain a good working environment, and ensure high reliability of cured products. Obtainable.

FIG. 3 is a cross-sectional view of the camera module.

Embodiments of the present invention will be described in detail below.

The resin composition of the present invention contains at least one type of each of a 2-methylene-1,3-dicarbonyl compound and a tertiary amine compound. The components contained in the composition of the present invention will be explained below.

で表される構造単位を少なくとも１つ有し、かつ分子量が１８０～１００００である化合物である。
２－メチレン－１，３－ジカルボニル化合物は、上記式（Ｉ）の構造単位を１つ又は２つ以上含む。ある態様においては、２－メチレン－１，３－ジカルボニル化合物は、上記式（Ｉ）の構造単位を２つから６つ、好ましくは２つ含む。 [(a) 2-methylene-1,3-dicarbonyl compound]
The resin composition of the present invention contains at least one 2-methylene-1,3-dicarbonyl compound (component (a)). Each of these 2-methylene-1,3-dicarbonyl compounds has the following formula (I):

A compound having at least one structural unit represented by the formula and having a molecular weight of 180 to 10,000.
The 2-methylene-1,3-dicarbonyl compound contains one or more structural units of the above formula (I). In one embodiment, the 2-methylene-1,3-dicarbonyl compound contains 2 to 6, preferably 2, structural units of formula (I) above.

Since the above 2-methylene-1,3-dicarbonyl compound contains the structural unit of the above formula (I), it is polymerized by the action of the tertiary amine compound described below, so it is the main component of the one-component adhesive. It can be used as When the above-mentioned 2-methylene-1,3-dicarbonyl compound contains a compound having two or more structural units of the above formula (I) (polyfunctional), crosslinking occurs during curing, and the cured product is not easily machined at high temperatures. Improvements in physical properties such as improved properties are expected.

The resin composition of the present invention contains one or more types, preferably two or more types of 2-methylene-1,3-dicarbonyl compounds. At least one of the 2-methylene-1,3-dicarbonyl compounds contained in the resin composition of the present invention has a molecular weight of 180 to 10,000, more preferably 180 to 5,000, still more preferably 180 to 2,000, More preferably from 200 to 1,500, still more preferably from 240 to 1,500, particularly preferably from 250 to 1,500, most preferably from 260 to 1,500. The molecular weight of the 2-methylene-1,3-dicarbonyl compound contained in the resin composition and each when the entire resin composition or the entire 2-methylene-1,3-dicarbonyl compound in the resin composition is taken as 1. The mass content of the 2-methylene-1,3-dicarbonyl compound can be determined, for example, by reverse-phase high performance liquid chromatography (reverse-phase HPLC) using an ODS column as a column, a mass spectrometer (MS) and a PDA as a detector. (Detection wavelength: 190 to 800 nm) or calibrated using ELSD. When the molecular weight of the 2-methylene-1,3-dicarbonyl compound is less than 180, the volatility of the compound becomes high and the working environment deteriorates. In addition, volatile components tend to cause deposits (solid matter) to be generated on surrounding members. On the other hand, if the molecular weight of the 2-methylene-1,3-dicarbonyl compound exceeds 10,000, the viscosity of the composition will increase, resulting in lower workability and other disadvantages such as limiting the amount of filler added. .

The 2-methylene-1,3-dicarbonyl compound according to the present invention preferably contains a polyfunctional 2-methylene-1,3-dicarbonyl compound (polyfunctional component) from the viewpoint of heat resistance of the cured product. . Here, polyfunctional means that the 2-methylene-1,3-dicarbonyl compound contains two or more structural units of the above formula (I). The number of structural units of the above formula (I) contained in a 2-methylene-1,3-dicarbonyl compound is referred to as the "number of functional groups" of the 2-methylene-1,3-dicarbonyl compound. Among 2-methylene-1,3-dicarbonyl compounds, those with one functional group are called "monofunctional," those with two functional groups are called "bifunctional," and those with three functional groups are called "trifunctional." call.
When the 2-methylene-1,3-dicarbonyl compound contains a polyfunctional component, the content of the polyfunctional component is determined by the total mass of the 2-methylene-1,3-dicarbonyl compound from the viewpoint of mechanical properties at high temperatures. It is preferably 1 to 100% by mass, more preferably 5 to 95% by mass, even more preferably 5 to 90% by mass, particularly preferably 10 to 90% by mass, Most preferably it is 10-80% by weight. If the content of the polyfunctional component is less than 0.1% by mass, crosslinking will not be sufficiently formed during curing, and the mechanical properties of the cured product at high temperatures (above the softening point) will be significantly impaired.
When the resin composition of the present invention contains a polyfunctional component, the cured product forms a network-like crosslinked structure, so it does not flow even at high temperatures, especially at temperatures above the glass transition temperature, and has a certain storage elasticity. hold the rate. The storage modulus of the cured product at high temperatures can be evaluated, for example, by dynamic mechanical analysis (DMA). Generally, when a cured product having a crosslinked structure is evaluated by DMA, a region called a plateau in which the temperature change in storage modulus is relatively small is observed over a wide range in the temperature range above the glass transition temperature. The storage modulus in this plateau region is evaluated as a crosslinking density, that is, an amount related to the content of the polyfunctional component in the resin composition.

Further, the 2-methylene-1,3-dicarbonyl compound according to the present invention preferably contains an ester structure from the viewpoint of reactivity.

The resin composition of the present invention can contain at least one 2-methylene-1,3-dicarbonyl compound containing two or more structural units represented by the above formula (I).

The mass ratio of the 2-methylene-1,3-dicarbonyl compound contained in the resin composition of the present invention to the entire composition is 0.05 to 0.999, more preferably 0.15 to 0.999, More preferably, it is 0.50 to 0.999. When the mass ratio of the 2-methylene-1,3-dicarbonyl compound contained in the composition of the present invention to the entire composition is less than 0.05, the 2-methylene-1,3-dicarbonyl compound is contained in the composition. There is a concern that it will not be distributed throughout, resulting in uneven curing.

（式中、
Ｘ^１及びＸ^２は、各々独立に、単結合、Ｏ又はＮＲ^３（式中、Ｒ^３は、水素又は１価の炭化水素基を表す）を表し、
Ｒ^１及びＲ^２は、各々独立に、水素、１価の炭化水素基又は下記式（ＩＩＩ）：

（式中、
Ｘ^３及びＸ^４は、各々独立に、単結合、Ｏ又はＮＲ^５（式中、Ｒ^５は、水素又は１価の炭化水素基を表す）を表し、
Ｗは、スペーサーを表し、
Ｒ^４は、水素又は１価の炭化水素基を表す）を表す）
で表される。 In some embodiments, the 2-methylene-1,3-dicarbonyl compound has the following formula (II):

(In the formula,
X ¹ and X ² each independently represent a single bond, O or NR ³ (wherein R ³ represents hydrogen or a monovalent hydrocarbon group),
R ¹ and R ² are each independently hydrogen, a monovalent hydrocarbon group, or the following formula (III):

(In the formula,
X ³ and X ⁴ each independently represent a single bond, O or NR ⁵ (wherein R ⁵ represents hydrogen or a monovalent hydrocarbon group),
W represents a spacer,
^R4 represents hydrogen or a monovalent hydrocarbon group)
It is expressed as

（式中、
Ｒ^１及びＲ^２は、各々独立に、水素、１価の炭化水素基又は下記式（Ｖ）：

（式中、
Ｗは、スペーサーを表し、
Ｒ^４は、水素又は１価の炭化水素基を表す）を表す）
で表される。 In some embodiments, the 2-methylene-1,3-dicarbonyl compound has the following formula (IV):

(In the formula,
R ¹ and R ² are each independently hydrogen, a monovalent hydrocarbon group, or the following formula (V):

(In the formula,
W represents a spacer,
^R4 represents hydrogen or a monovalent hydrocarbon group)
It is expressed as

（式中、
Ｒ^１１は、下記式（ＶＩＩ）：

で表される１，１－ジカルボニルエチレン単位を表し、
それぞれのＲ^１２は、各々独立に、スペーサーを表し、
Ｒ^１３及びＲ^１４は、各々独立に、水素又は１価の炭化水素基を表し、
Ｘ^１１並びにそれぞれのＸ^１２及びＸ^１３は、各々独立に、単結合、Ｏ又はＮＲ^１５（式中、Ｒ^１５は、水素又は１価の炭化水素基を表す）を表し、
それぞれのｍは、各々独立に、０又は１を表し、
ｎは、１以上２０以下の整数を表す）
で表されるジカルボニルエチレン誘導体である。 In another embodiment, the 2-methylene-1,3-dicarbonyl compound has the following formula (VI):

(In the formula,
R ¹¹ is the following formula (VII):

represents a 1,1-dicarbonylethylene unit represented by
each R ¹² independently represents a spacer;
R ¹³ and R ¹⁴ each independently represent hydrogen or a monovalent hydrocarbon group,
X ¹¹ and each X ¹² and X ¹³ each independently represent a single bond, O or NR ¹⁵ (wherein R ¹⁵ represents hydrogen or a monovalent hydrocarbon group),
Each m independently represents 0 or 1,
n represents an integer from 1 to 20)
It is a dicarbonylethylene derivative represented by

In this specification, a monovalent hydrocarbon group refers to a group produced by removing one hydrogen atom from a carbon atom of a hydrocarbon. Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkyl-substituted cycloalkyl group, an aryl group, an aralkyl group, and an alkaryl group, some of which include N, Heteroatoms such as O, S, P and Si may also be included.

The above monovalent hydrocarbon groups are alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, allyl, alkoxy, alkylthio, hydroxyl, nitro, amide, azide, cyano, acyloxy, carboxy, sulfoxy, acryloxy, siloxy, and epoxy. , or may be substituted with an ester.
The monovalent hydrocarbon group is preferably an alkyl group, a cycloalkyl group, an aryl group, or an alkyl group substituted with a cycloalkyl group, and more preferably an alkyl group, a cycloalkyl group, or a cycloalkyl group. is an alkyl group substituted with

There is no particular limitation on the number of carbon atoms in the alkyl group, alkenyl group, and alkynyl group (hereinafter collectively referred to as "alkyl group, etc."). The alkyl group usually has 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, more preferably 4 to 7 carbon atoms, and particularly preferably 5 to 6 carbon atoms. Further, the number of carbon atoms in the alkenyl group and the alkynyl group is usually 2 to 12, preferably 2 to 10, more preferably 3 to 8, more preferably 3 to 7, particularly preferably 3 to 6. When the alkyl group has a cyclic structure, the number of carbon atoms in the alkyl group is usually 4 to 12, preferably 4 to 10, more preferably 5 to 8, more preferably 6 to 8.

There is no particular limitation on the structure of the above alkyl group, etc. The alkyl group and the like may be linear or have a side chain. The alkyl group and the like may have a chain structure or a cyclic structure (cycloalkyl group, cycloalkenyl group, and cycloalkynyl group). The above alkyl group and the like may have one or more types of other substituents. For example, the alkyl group and the like may have a substituent containing an atom other than a carbon atom or a hydrogen atom. Further, the alkyl group and the like may contain one or more atoms other than carbon atoms and hydrogen atoms in the chain structure or the cyclic structure. Examples of atoms other than the carbon atom and hydrogen atom include one or more of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom.

Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, Examples include isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, and 2-ethylhexyl group. Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a 2-methylcyclohexyl group. Examples of the alkenyl group include a vinyl group, an allyl group, and an isopropenyl group. A specific example of the cycloalkenyl group is a cyclohexenyl group. Specific examples of the 2-methylene-1,3-dicarbonyl compounds include dibutylmethylene malonate, dipentylmethylene malonate, dihexylmethylene malonate, dicyclohexylmethylene malonate, ethyl octyl methylene malonate, and propylhexyl methylene malonate. , 2-ethylhexyl-ethylmethylene malonate, ethylphenyl-ethylmethylene malonate, and the like. These are preferred because of their low volatility and high reactivity. From the viewpoint of ease of handling, dihexyl methylene malonate and dicyclohexyl methylene malonate are particularly preferred.

In this specification, a spacer refers to a divalent hydrocarbon group, and more specifically, a cyclic, linear, or branched substituted or unsubstituted alkylene group. There is no particular limitation on the number of carbon atoms in the alkylene group. The alkylene group usually has 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 4 to 8 carbon atoms. Here, the alkylene group may contain a group containing a heteroatom selected from N, O, S, P, and Si in the middle, if desired. Further, the alkylene group may have an unsaturated bond. In some embodiments, the spacer is an unsubstituted alkylene group having 4 to 8 carbon atoms. Preferably, the spacer is a linear substituted or unsubstituted alkylene group, more preferably represented by the formula -(CH ₂ ) _n -, where n is an integer from 2 to 10, preferably from 4 to 8. is an alkylene group having a structure in which the carbon atoms at both ends bond to the remaining portion of the 2-methylene-1,3-dicarbonyl compound.
Specific examples of the divalent hydrocarbon group as the spacer include, but are not limited to, 1,4-n-butylene group and 1,4-cyclohexylene dimethylene group.

When the 2-methylene-1,3-dicarbonyl compound has a spacer, the terminal monovalent hydrocarbon group preferably has 6 or less carbon atoms. That is, when the above 2-methylene-1,3-dicarbonyl compound is represented by the above formula (II) or (IV), R ⁴ in the above formula (III) or (V) has 1 to 6 carbon atoms. It is preferably alkyl, provided that when one of R ¹ and R ² is represented by the above formula (III) or formula (V), the other of R ¹ and R ² is an alkyl having 1 to 6 carbon atoms. It is preferable that there be. In this case, in the above formula (II) or (IV), both R ¹ and R ² may be represented by the above formula (III) or formula (V), but preferably one of R ¹ and R ² only is represented by the above formula (III) or formula (V). Preferably, the 2-methylene-1,3-dicarbonyl compound is represented by the formula (IV).
A particularly preferred compound is one in which one of R ¹ or R ² in the above formula (IV) is an ethyl group, n-hexyl group, or cyclohexyl group, the other is represented by the above formula (V), and W is Examples include compounds in which R 4 is either a 1,4-n-butylene group or a 1,4-cyclohexylene dimethylene group, and R ⁴ is an ethyl group, an n-hexyl group, or a cyclohexyl group. In addition, as another particularly preferable compound, R ¹ and R ² in the above formula (IV) are represented by the above formula (V), and W is a 1,4-n-butylene group or a 1,4-cyclohexylene dimethylene group. Examples include compounds in which R ⁴ is an ethyl group, an n-hexyl group, or a cyclohexyl group.

2-methylene-1,3-dicarbonyl compounds with different molecular weights are available from SIRRUS Inc., Ohio, USA. The synthesis method thereof is disclosed in published patent publications such as WO2012/054616, WO2012/054633, and WO2016/040261. When both ends of the structural unit represented by the above formula (I) contained in the 2-methylene-1,3-dicarbonyl compound are bonded to oxygen atoms, diols or By using a known method such as transesterification with a polyol, a larger molecular weight 2-methylene-1 in which a plurality of structural units represented by the above formula (I) are bonded via an ester bond and the above spacer is obtained. ,3-dicarbonyl compounds can be produced. The 2-methylene-1,3-dicarbonyl compound produced in this way has R ¹ and R ² in the above formula (II) or the above formula (IV), the above formula (III) or the above formula (V) R ⁴ in the formula (VI), and R ¹⁴ and R ¹³ in the above formula (VI) may contain a hydroxy group.

[(b) Tertiary amine compound]
The resin composition of the present invention contains at least one tertiary amine compound (component (b)). This tertiary amine compound acts as an initiator, and when the resin composition is cured by Michael addition of the 2-methylene-1,3-dicarbonyl compound (component (a)) to the olefinic carbon. This compound is expected to contribute to the initiation of the reaction. Each of these tertiary amine compounds has the formula [NR(CH ₃ )] _n -R' (wherein each R independently represents a monovalent hydrocarbon group, n is an integer of 1 or more, R' represents an n-valent organic group) and has a molecular weight of 100 to 1,000. Furthermore, at least one of the disubstituted amino groups NR(CH ₃ )- in the above formula has a pKa of 8.0 or more. In the present invention, the tertiary amine compound may be used alone or in combination of two or more.

The molecular weight of the tertiary amine compound is 100 to 1000, preferably 100 to 500, and more preferably 110 to 300. When the molecular weight of the tertiary amine compound is less than 100, its volatility is high, so there are concerns that it may affect peripheral members and change the physical properties of the cured product. When the molecular weight of the tertiary amine compound exceeds 1,000, there are concerns that the tertiary amine compound may increase in viscosity, decrease in dispersibility in the resin composition, and the like.

The monovalent hydrocarbon group as the hydrocarbon group R is the same as that defined for the component (a). In addition, when R contains an aromatic ring, if the aromatic ring is directly bonded to the nitrogen atom in the disubstituted amino group, the pKa of the disubstituted amino group tends to be lowered (basicity becomes weaker). Please note the following points. In one embodiment, the tertiary amine compound does not include a structure in which the aromatic ring in R is directly bonded to the nitrogen atom in the disubstituted amino group.

The structure of the organic group R' in the tertiary amine compound is not particularly limited as long as it is an organic group (eg, a hydrocarbon group) that gives the tertiary amine compound a molecular weight of 100 to 1,000. The organic group R' may have a linear, branched, or cyclic structure, and may have an unsaturated bond and/or an aromatic ring. The above R may be taken together to form a ring. In addition, when R' contains an aromatic ring, if the aromatic ring is directly bonded to the nitrogen atom in the disubstituted amino group, the pKa of the disubstituted amino group will be lowered (basicity will be weakened). It is necessary to pay attention to the trends. In one embodiment, the tertiary amine compound does not include a structure in which the aromatic ring in R' is directly bonded to the nitrogen atom in the disubstituted amino group. In addition, the organic group R' may be unsubstituted or substituted with a substituent as long as the effects of the present invention are not impaired, and atoms other than carbon atoms and hydrogen atoms (oxygen atoms, nitrogen atoms, sulfur atoms, atom, phosphorus atom, silicon atom, etc.).

In the tertiary amine compound, n may be 1 or an integer of 2 or more. In other words, the organic group R' may be a monovalent organic group bonded to one of the disubstituted amino groups, or may be a divalent or higher organic group bonded to two or more of the disubstituted amino groups. There may be. Therefore, for example, a compound having multiple types of basic moieties corresponding to the disubstituted amino group, such as 2,6,10-trimethyl-2,6,10-triazaundecane (TMTAU), can also be used as the tertiary amino group. Included in amine compounds. However, from the viewpoint of adjusting physical properties, it may be desirable to avoid guanidine compounds. In some embodiments, the tertiary amine compound does not include a guanidine backbone. In the tertiary amine compound, n is preferably 1 to 3, more preferably 1 to 2, and most preferably 1.

In addition to the disubstituted amino group, the tertiary amine compound has a disubstituted amino group that does not correspond to the disubstituted amino group, for example, a disubstituted amino group having two non-methyl hydrocarbon groups in the organic group R'. May contain. The tertiary amine compound may further contain an unsubstituted or monosubstituted amino group, but the active hydrogen atoms (exchangeable hydrogen) contained therein may inhibit the polymerization reaction. Therefore, the tertiary amine compound preferably does not contain an unsubstituted or monosubstituted amino group. For the same reason, it is preferable that the tertiary amine compound does not contain a hydroxy group or a mercapto group. Further, when a carbon atom directly bonded to a nitrogen atom has an unsaturated bond, the lone pair of electrons on the nitrogen atom becomes delocalized, so that the pKa tends to be lower (basicity becomes weaker). These unsaturated bonds include carbon atom-carbon atom, carbon atom-nitrogen atom, and carbon atom-oxygen atom bonds. For example, a disubstituted amino group in which an aromatic ring or a carbonyl group is directly bonded to a nitrogen atom tends to have a low pKa (weak basicity). In one embodiment, the tertiary amine compound does not include a structure in which an aromatic ring or a carbonyl group is directly bonded to the nitrogen atom of the disubstituted amino group.

Generally, the basicity of a basic compound such as an amine is determined by the acid dissociation index, which is the common logarithm value (-logKa) of the reciprocal of the acid dissociation constant Ka for the equilibrium between the basic compound and the corresponding conjugate acid. It can be evaluated (estimated) by pKa. In this specification, the pKa of the conjugate acid of the tertiary amine compound (or the disubstituted amino group contained therein) may be simply referred to as the pKa of the compound or group.
In the tertiary amine compound, at least one of the disubstituted amino groups has a pKa of 8.0 or more, preferably 9.0 or more, more preferably 10.0 or more, and most preferably is 11.0 or more. If the pKa of all the disubstituted amino groups is less than 8.0, the action of the tertiary amine compound as an initiator will be insufficient, and the resin composition will not be cured within a predetermined time. This is because, in the resin composition of the present invention, the molecular weight of the 2-methylene-1,3-dicarbonyl compound contained in the component (a) is 180 or more.

The fact that the 2-methylene-1,3-dicarbonyl compound has a molecular weight of 180 or more corresponds to the fact that the compound has a relatively large substituent. In conjunction with this, steric hindrance near the olefin carbon is relatively large, making it relatively difficult for the tertiary amine compound to approach the olefin carbon. Therefore, in order for the tertiary amine compound to exhibit a sufficiently strong effect as an initiator, the tertiary amine compound must exhibit some degree of strong basicity, that is, the pKa of the disubstituted amino group must be at least a certain level. Otherwise, the action of the tertiary amine compound as an initiator will be insufficient and the reaction will be difficult to start.

The above acid dissociation index pKa can be appropriately determined by methods known to those skilled in the art, such as electrochemical methods and spectroscopic methods. In this specification, "pKa" is defined as using ChemAxon's software MarvinSketch 17.22.0 at a temperature of 298K, a mode of macro, and an acid/base prefix of static, unless otherwise specified. Refers to the pKa value estimated when water is used as the solvent based on the chemical structure. When the tertiary amine compound contains a plurality of basic sites corresponding to the disubstituted amino group, the largest pKa value is adopted as the pKa value of the amine compound.

Since the hydrocarbon group with the least steric hindrance is the methyl group, when R in the disubstituted amino group is a methyl group, that is, when the disubstituted amino group is a dimethylamino group, the steric hindrance near the nitrogen atom is the lowest. small. In this case, the pKa of the disubstituted amino group, which is necessary for the tertiary amine compound to exhibit a sufficiently strong action as an initiator, is slightly lower than when R is not a methyl group. When R in the disubstituted amino group is a methyl group, it is particularly preferable that the pKa of the disubstituted amino group is 8.5 or more.

On the other hand, when R in the disubstituted amino group is a hydrocarbon group other than a methyl group (non-methyl hydrocarbon group), the steric hindrance near the nitrogen atom becomes greater than when R is a methyl group. . Therefore, in this case, in order to sufficiently strengthen the action of the tertiary amine compound as an initiator, the disubstituted amino group must have a higher pKa value, that is, a stronger It is necessary to show basicity. More specifically, when R in the disubstituted amino group is a non-methyl hydrocarbon group, it is preferable that the pKa of the disubstituted amino group is 9.0 or more.

If all the substituents on the disubstituted amino group are non-methyl hydrocarbon groups, the steric hindrance near the nitrogen atom will be too large, so the action of the tertiary amine compound as an initiator should be made sufficiently strong. is difficult.

Among the tertiary amine compounds used in the present invention, examples of those having one dimethylamino group as the disubstituted amino group include dimethyl n-butylamine, dimethylisobutylamine, dimethyl s-butylamine, dimethyl t-butylamine, Dimethyl n-hexylamine, dimethylisohexylamine, dimethylcyclohexylamine, dimethyl n-octylamine, dimethylisooctylamine, dimethyl n-decylamine, dimethylisodecylamine, dimethyl n-dodecylamine, dimethylisododecylamine, dimethylbenzylamine Examples include, but are not limited to, the following.

Among the tertiary amine compounds used in the present invention, examples of compounds having one group other than dimethylamino group as the disubstituted amino group include dimethyl A tertiary compound in which one of the two methyl groups on the amino group is substituted with a non-methyl hydrocarbon group (for example, the non-methyl hydrocarbon group in the tertiary amine compound having one dimethylamino group) Examples include, but are not limited to, amine compounds.

Among the tertiary amine compounds used in the present invention, examples of compounds having two or more dimethylamino groups as the disubstituted amino group include tetramethylethylenediamine, tetramethylpropylenediamine, 2,6,10-trimethyl-2 , 6,10-triazaundecane (TMTAU) and the like, but are not limited thereto.

（式中、Ｒ^１０１及びＲ^１０２は各々独立に、１価の炭化水素基（前記成分（ａ）について定義されたものと同様）を表す）
で表される構造を有する。Ｒ^１０１及びＲ^１０２は各々、炭素数１～３０であるものが好ましく、炭素数１～２０であるものがより好ましく、炭素数１～１２であるものが特に好ましい。Ｒ^１０１及びＲ^１０２はそれぞれ独立に、あるいは共同して窒素原子周辺の立体障害をもたらす。このため、Ｒ^１０１及びＲ^１０２の一方が炭素数４以上のような大きな基であっても、他方がエチル基のような比較的炭素数の少ない基であると、開始剤として十分な作用が得られることがある。また、Ｒ^１０１及びＲ^１０２が共に炭素数６以上の基であっても、芳香環やシクロアルキル基のような環状構造を有する場合には、分子運動が環状構造を有しない場合に比べて制限されることから、開始剤として十分な作用が得られることがある。さらに、Ｒ^１０１及びＲ^１０２が互いに結合して環状構造を形成している場合、両者の総炭素数が４以上であっても窒素原子周辺の立体障害は比較的小さいことから、開始剤として十分な作用が得られることがある。 In some embodiments, the tertiary amine compound has the following formula:

(wherein R ¹⁰¹ and R ¹⁰² each independently represent a monovalent hydrocarbon group (as defined for component (a) above))
It has the structure represented by Each of R ¹⁰¹ and R ¹⁰² preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms. R ¹⁰¹ and R ¹⁰² each independently or jointly provide steric hindrance around the nitrogen atom. Therefore, even if one of R ¹⁰¹ and R ¹⁰² is a large group with 4 or more carbon atoms, if the other is a group with a relatively small number of carbon atoms such as an ethyl group, it will not function sufficiently as an initiator. There are things you can get. Furthermore, even if both R ¹⁰¹ and R ¹⁰² are groups with 6 or more carbon atoms, if they have a cyclic structure such as an aromatic ring or a cycloalkyl group, molecular movement will be more restricted than when they do not have a cyclic structure. Therefore, sufficient action as an initiator may be obtained. Furthermore, when R ¹⁰¹ and R ¹⁰² combine with each other to form a cyclic structure, the steric hindrance around the nitrogen atom is relatively small even if the total number of carbon atoms in both is 4 or more, so it is sufficient as an initiator. Some effects may be obtained.

In the present invention, if the tertiary amine compound is solid when the resin composition is cured, the reaction will not proceed uniformly throughout the composition, but will proceed substantially only on the surface of the tertiary amine compound. Curing becomes uneven. For this reason, the tertiary amine compound is preferably liquid at 80°C, and more preferably liquid at 25°C.

The tertiary amine compound used in the present invention may be made inactive as an initiator by separation or latentization, and may be activated by any stimulus such as heat, light, mechanical shearing, etc. . More specifically, the tertiary amine compound may be in the form of a latent curing catalyst such as a microcapsule, ionically dissociated type, inclusion type, etc., and can be cured by heat, light, electromagnetic waves, ultrasound, or physical shearing. It may also be in a form that generates a base. Moreover, the resin composition of the present invention can also be used as a two-component adhesive.

In the present invention, the content of the tertiary amine compound is preferably 0.01 mol% to 30 mol% with respect to the total amount (100 mol%) of the 2-methylene-1,3-dicarbonyl compound in the resin composition. , more preferably 0.01 mol% to 10 mol%. If the content of the tertiary amine compound is less than 0.01 mol%, curing becomes unstable. On the other hand, when the content of the tertiary amine compound is more than 30 mol%, a large amount of the tertiary amine compound that does not form a chemical bond with the resin matrix remains in the cured product, resulting in a decrease in the physical properties of the cured product. or bleed.

The resin composition of the present invention may contain the components described below in addition to the above components (a) and (b), if necessary.

[(c) Inorganic filler]
The resin composition of the present invention can contain an inorganic filler (component (c)). Component (c) includes silica fillers such as colloidal silica, hydrophobic silica, fine silica, and nanosilica, metal oxides such as calcium carbonate, alumina, and zinc oxide, metals such as nickel, copper, and silver, acrylic beads, and glass beads. , urethane beads, bentonite, acetylene black, Ketjen black, etc. Among these, silica filler is preferred because it can increase the amount of filler. The inorganic filler of component (c) may be surface-treated with a silane coupling agent or the like. When a surface-treated filler is used, an effect of preventing filler aggregation is expected. The inorganic filler of component (c) may be used alone or in combination of two or more.

In addition, the average particle size (if not granular, the average maximum diameter) of the inorganic filler of component (c) is not particularly limited, but it is preferable that the filler be included in the resin composition. It is preferable for uniform dispersion, and also because it has excellent injectability when the resin composition is used as a liquid sealant such as an adhesive or an underfill. If it is less than 0.01 μm, the viscosity of the resin composition will increase, and there is a risk that the injectability will deteriorate when used as a liquid sealant such as an adhesive or an underfill. If it exceeds 50 μm, it may be difficult to uniformly disperse the filler in the resin composition. Further, from the viewpoint of protecting the copper wire from heat stress of the resin composition after curing, the average particle size of component (c) is more preferably 0.6 to 10 μm. Commercially available products include high-purity synthetic spherical silica manufactured by Admatex (product name: SE5200SEE, average particle size: 2 μm; product name: SO-E5, average particle size: 2 μm; product name: SO-E2, average particle size: 0.6 μm). , Ryumori silica (product name: FB7SDX, average particle size: 10 μm), Micron silica (product name: TS-10-034P, average particle size: 20 μm), and the like. Here, the average particle size of the inorganic filler is measured using a dynamic light scattering nanotrack particle size analyzer.

Component (c) may be insulating or conductive. The content of the inorganic filler as component (c) is preferably 0 to 95 parts by mass based on a total of 100 parts by mass of all components of the resin composition when the inorganic filler is insulating. More preferably 0 to 85 parts by weight, still more preferably 0 to 50 parts by weight. When the amount is 0 to 50 parts by mass, deterioration of the injectability of the resin composition can be avoided when the resin composition is used as a liquid sealant such as underfill. When the amount is 10 to 95 parts by mass, the linear expansion coefficient of the resin composition can be lowered. In addition, from the viewpoint of electrical conductivity, the content of the inorganic filler (component (c)) is preferably 50 to 95 parts by mass when the inorganic filler is electrically conductive so that it can be used as a conductive paste. preferable.

[(d) Stabilizer]
The resin composition of the present invention may also contain a stabilizer (component (d)).
Component (d) is added to improve the stability of the resin composition during storage, and is added to suppress the occurrence of polymerization reactions caused by unintended radicals or basic components. A 2-methylene-1,3-dicarbonyl compound may generate radicals from itself with a low probability, and an unintended radical polymerization reaction may occur using the radicals as a starting point. Furthermore, the 2-methylene-1,3-dicarbonyl compound may undergo an anionic polymerization reaction if a very small amount of a basic component is mixed therein. By adding component (d), it is possible to suppress the occurrence of such unintended polymerization reactions due to radicals and basic components.

As component (d), known components can be used, such as strong acids and radical scavengers. Specific examples of component (d) include trifluoromethanesulfonic acid, maleic acid, methanesulfonic acid, difluoroacetic acid, trichloroacetic acid, phosphoric acid, dichloroacetic acid, N-nitroso-N-phenylhydroxylamine aluminum, and triphenylphosphine. , 4-methoxyphenol, and hydroquinone. Among these, the preferred component (d) is at least one selected from maleic acid, methanesulfonic acid, N-nitroso-N-phenylhydroxylamine aluminum, and 4-methoxyphenol. Further, as the component (d), known components disclosed in JP-A No. 2010-117545, JP-A No. 2008-184514, etc. can also be used. Component (d) may be used alone or in combination of two or more.

[(e) Surface treatment agent]
The resin composition of the present invention may also contain a surface treating agent (component (e)).
Component (e) is not particularly limited, but typically a coupling agent can be used. A coupling agent has two or more different functional groups in its molecule, one of which is a functional group that chemically bonds with an inorganic material, and the other one that chemically bonds with an organic material. It is a functional group. When the adhesive contains a coupling agent, the adhesion of the adhesive to a substrate or the like is improved.

Examples of coupling agents include, but are not limited to, silane coupling agents, aluminum coupling agents, titanium coupling agents, and the like. One type of coupling agent may be used, or two or more types may be used in combination.

Examples of functional groups possessed by the silane coupling agent include vinyl group, epoxy group, styryl group, methacrylic group, acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, isocyanate group, etc. I can do it.

[(f) Pigment]
The resin composition of the present invention may contain a pigment (component (f)).
By including component (f), the chromaticity of the resin composition of the present invention can be adjusted. Component (f) is not particularly limited, and for example, carbon black, titanium black such as titanium nitride, black organic pigment, color mixing organic pigment, inorganic pigment, etc. can be used. Black organic pigments include perylene black, aniline black, etc., and color mixture organic pigments include at least two or more pigments selected from red, blue, green, purple, yellow, magenta, cyan, etc. to create a pseudo-black color. Inorganic pigments include graphite, metal fine particles such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, metal oxides, composite oxides, metal sulfides, and metals. Examples include nitrides. These may be used alone or in combination of two or more. Component (f) is preferably carbon black or titanium black.

[(g) Plasticizer]
The resin composition of the present invention may contain a plasticizer (component (g)).
As component (g), any known plasticizer can be blended. Component (g) can improve moldability and adjust the glass transition temperature. As component (g), those having good compatibility and being difficult to bleed can be used.
Examples of component (g) include phthalic acid esters such as di-n-butyl phthalate, di-n-octyl phthalate, bis(2-ethylhexyl) phthalate, di-n-decyl phthalate, and diisodecyl phthalate; - Adipic acid esters such as ethylhexyl) adipate and di-n-octyl adipate; Sebacic acid esters such as bis(2-ethylhexyl) sebacate and di-n-butyl sebacate; Azelaic acid esters such as bis(2-ethylhexyl) azelate Paraffins such as chlorinated paraffin; Glycols such as polypropylene glycol; Epoxy-modified vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; Phosphate esters such as trioctyl phosphate and triphenyl phosphate; Phosphite esters such as phite; Ester oligomers such as esters of adipic acid and 1,3-butylene glycol; Low molecular weight polymers such as low molecular weight polybutene, low molecular weight polyisobutylene, and low molecular weight polyisoprene; Process oil , oils such as naphthenic oils, and the like. Component (g) may be used alone or in combination of two or more.

The resin composition of the present invention contains components (c) to (g) as necessary in addition to the 2-methylene-1,3-dicarbonyl compound and the tertiary amine compound. The composition of the invention can be prepared by mixing these components. A known device can be used for mixing. For example, they can be mixed using a known device such as a Henschel mixer or a roll mill. These components may be mixed at the same time, or some may be mixed first and the rest may be mixed later.

[vapor pressure]
The 2-methylene-1,3-dicarbonyl compound contained in the resin composition of the present invention preferably has a vapor pressure of 0.05 mmHg or less at 25°C, more preferably 0.01 mmHg or less, and It is particularly preferred that it be .001 mmHg or less.

In the present invention, the vapor pressure of a compound such as a 2-methylene-1,3-dicarbonyl compound is a value estimated by the Y-MB method using commercially available software HSPiP (5th Edition 5.0.04). be.
Further, in the present invention, the vapor pressure of the tertiary amine compound can also be estimated by the same method. The tertiary amine compound contained in the composition of the present invention preferably has a vapor pressure at 25° C. of 100 mmHg or less, more preferably 10 mmHg or less, and particularly preferably 1 mmHg or less.

The resin composition of the present invention may contain components other than the above-mentioned 2-methylene-1,3-dicarbonyl compound, tertiary amine compound, and (c) to (g), for example, to the extent that the effects of the present invention are not impaired. It may contain a flame retardant, an ion trapping agent, an antifoaming agent, a leveling agent, a foam-breaking agent, and the like.

The resin composition of the present invention can be used as an adhesive or a sealant. In particular, it can be used as a one-component resin composition, a one-component adhesive, or a sealant. Furthermore, it can be used as a solvent-free one-component resin composition, a solvent-free one-component adhesive, or a sealant. Specifically, the resin composition of the present invention is suitable for adhesion and sealing of electronic components. More specifically, the resin composition of the present invention can be used for camera module components, adhesion, and sealing, and is particularly suitable for adhesion of sensor modules such as image sensor modules. This is because the resin composition of the present invention has very little volatile components that contaminate the surroundings, and therefore does not easily generate deposits (solid matter).

For example, as shown in FIG. 1, the resin composition of the present invention can be used to bond an IR cut filter 20 and a printed wiring board 24. The resin composition of the present invention can be used for bonding the image sensor 22 and the printed wiring board 24. The resin composition of the present invention can be used for bonding the support 18 and the printed wiring board 24. A jet dispenser, an air dispenser, etc. can be used to supply the resin composition to the surface to be adhered. The resin composition of the present invention can be cured at room temperature without heating. The resin composition of the present invention can also be cured, for example, by heating at a temperature of 25 to 80°C. The heating temperature is preferably 50 to 80°C. The heating time is, for example, 0.5 to 4 hours.

The resin composition of the present invention can also be used for sensor modules such as image sensor modules other than camera modules. For example, it can be used for bonding and sealing parts of sensor modules such as image sensor modules that may be incorporated into fingerprint authentication devices, face authentication devices, scanners, medical equipment, etc.

Moreover, the resin composition of the present invention can also be used as a constituent material of a film or prepreg. In particular, the resin composition of the present invention is suitable for use as a coverlay film for protecting wiring patterns, an interlayer adhesive film for multilayer wiring boards, and a constituent material for prepregs. This is because the resin composition of the present invention has extremely low volatile components, so voids are less likely to occur. Moreover, the film or prepreg containing the resin composition of the present invention can be preferably used for electronic parts.

A prepreg containing the resin composition of the present invention can be produced by a known method, such as a hot melt method or a solvent method. When using the hot melt method, the resin composition of the present invention is coated on a release paper with good releasability without being dissolved in an organic solvent, and then it is laminated onto a sheet-like fiber base material, or a die coater is used. Prepreg can be manufactured by directly coating the material. In addition, when using the solvent method, first, the sheet-like fiber base material is immersed in a resin composition varnish in which the resin composition of the present invention is dissolved in an organic solvent, thereby impregnating the sheet-like fiber base material with the resin composition varnish. By drying the sheet-like fiber base material after that, a prepreg can be manufactured.

A film containing the resin composition of the present invention can be obtained from the resin composition of the present invention by a known method. For example, the resin composition of the present invention is diluted with a solvent to form a varnish, which is applied to at least one side of a support, dried, and then provided as a film attached to the support or a film peeled from the support. be able to.

The present invention also provides a cured product obtained by curing the resin composition of the present invention. In addition, in the present invention, a cured product obtained by curing an adhesive or a sealing material containing the resin composition of the present invention, and a cured product obtained by curing a film or prepreg containing the resin composition of the present invention is also provided.
Furthermore, the present invention also provides a semiconductor device comprising the cured product of the present invention, the cured product of the adhesive or sealant of the present invention, or the cured product of the film or prepreg of the present invention.

The present invention also provides a method for adhering a member constituting an electronic component, in which the resin composition of the present invention is applied to a member constituting the electronic component and bonded to another member constituting the electronic component. The electronic component is preferably a camera module component, more preferably an image sensor module. Also provided is a method of coating or injecting the resin composition of the present invention to adhere or seal electronic components or semiconductor elements onto a substrate. Furthermore, a method of sealing an electronic circuit formed on a substrate by applying the resin composition of the present invention onto the electronic circuit is also provided.

Examples and comparative examples of the present invention will be described below. The present invention is not limited to the following examples and comparative examples. In the following Examples and Comparative Examples, the proportions of components contained in the resin composition are shown in parts by mass.

[Estimation of vapor pressure]
For some embodiments of the 2-methylene-1,3-dicarbonyl compound used in the present invention, the vapor pressure at each temperature was estimated using HSPiP (5th Edition 5.0.04 Y-MB method). Table 1 shows the vapor pressure (unit: mmHg) at each temperature for the three types of 2-methylene-1,3-dicarbonyl compounds shown in Table 3.

表１より、分子量が１８０以上の２－メチレン－１，３－ジカルボニル化合物は蒸気圧が低く、特に２５℃における蒸気圧が０．０５mmHg以下であることがわかる。２５℃における蒸気圧が０．０５mmHg以下の２－メチレン－１，３－ジカルボニル化合物は、室温での硬化時に揮発が少なく、周囲部材への汚染が少ない。

Table 1 shows that 2-methylene-1,3-dicarbonyl compounds with a molecular weight of 180 or more have a low vapor pressure, particularly at 25° C., a vapor pressure of 0.05 mmHg or less. A 2-methylene-1,3-dicarbonyl compound having a vapor pressure of 0.05 mmHg or less at 25° C. evaporates less during curing at room temperature and causes less contamination to surrounding members.

The vapor pressures of some embodiments of the tertiary amine compounds used in the present invention were similarly estimated. Table 2 shows dimethyldodecylamine (DMDA), 2,6,10-trimethyl-2,6,10-triazaundecane (TMTAU), N,N-dimethylbenzylamine (DMBA), diethylmethylamine (DEMA), Vapor pressure ( Unit: mmHg).

表２より、分子量が１００未満の第三級アミン化合物（ＤＥＭＡ）は、蒸気圧が著しく高く、特に２５℃における蒸気圧が１００mmHgを超えることがわかる。このような第三級アミン化合物は揮発性が高いので、本発明における使用には適していない。

From Table 2, it can be seen that the tertiary amine compound (DEMA) with a molecular weight of less than 100 has a significantly high vapor pressure, and in particular, the vapor pressure at 25° C. exceeds 100 mmHg. Such tertiary amine compounds are highly volatile and are therefore not suitable for use in the present invention.

[Preparation of resin composition]
The raw materials for the resin compositions used in the following Examples and Comparative Examples are as follows.
2-methylene-1,3-dicarbonyl compound:
DHMM (manufactured by SIRRUS)
DCHMM (manufactured by SIRRUS)
CDM-XL (manufactured by SIRRUS)
The specific structure of the 2-methylene-1,3-dicarbonyl compound is as shown in the chemical formula in Table 3 below.

Tertiary amine compound:
DMDA dimethyldodecylamine
(Wako Pure Chemical Industries, Ltd., molecular weight: 213.4, pKa: 9.8)
TMTAU 2,6,10-trimethyl-2,6,10-triazaundecane
(Tokyo Kasei Kogyo Co., Ltd., molecular weight: 201.4, pKa: 9.5)
DMBA N,N-dimethylbenzylamine
(Wako Pure Chemical Industries, Ltd., molecular weight: 135.2, pKa: 8.9)
EMBA Ethylmethylbenzylamine
(Tokyo Kasei Kogyo Co., Ltd., molecular weight: 149.2, pKa: 9.2)
DCHMA N,N-dicyclohexylmethylamine
(Tokyo Kasei Kogyo Co., Ltd., molecular weight: 195.3, pKa: 11.2)
PMAN N,N,2,4,6-pentamethylaniline
(Tokyo Kasei Kogyo Co., Ltd., molecular weight: 163.3, pKa: 5.8)
DEBA diethylbenzylamine
(Wako Pure Chemical Industries, Ltd., molecular weight: 165.3, pKa: 9.5)
DEMA diethylmethylamine
(Wako Pure Chemical Industries, Ltd., molecular weight: 87.2, pKa: 10.0)
Among these tertiary amine compounds, DEBA does not have a disubstituted amino group to which a methyl group is bonded. DMDA, TMTAU, DMBA and PMAN have dimethylamino groups. Other tertiary amine compounds have a disubstituted amino group with one methyl group attached. The pKa value for TMTAU with multiple basic sites is for two dimethylamino groups that are equivalent to each other, which is the highest pKa value exhibited by those basic sites.

The above 2-methylene-1,3-dicarbonyl compound and tertiary amine compound in the amounts shown in Tables 4 and 5 (unit: g) were placed in a screw tube bottle made of borosilicate glass. The bottle was shaken vigorously for 3 minutes at room temperature (25°C) to thoroughly mix the contents. Thereafter, the time required for the contents of the screw tube bottle to virtually lose its fluidity was measured at room temperature (25° C.). The results are shown in Tables 4 and 5. Here, "actually losing fluidity" means that when the contents of the screw tube bottle are instantaneously tilted horizontally from an upright position, no obvious change in shape is observed under gravity for 10 seconds. Refer to the condition.

(Consideration of results)
Examples 1 to 3 contain at least one dimethylamino group, that is, a disubstituted amino group NR(CH ₃ )- in which R is a methyl group, and the pKa of the dimethylamino group is 8.0 or more. It has been shown that when a tertiary amine compound (DMDA, TMTAU, DMBA) is used as an initiator, gelation occurs in a very short time. Examples 6 to 8 show that the results are the same even when the type and number of the 2-methylene-1,3-dicarbonyl compound are varied.
Note that even tertiary amine compounds having such a structure are easily volatile when the molecular weight is less than 100 (trimethylamine in particular has extremely high volatility (gaseous at room temperature) and is extremely toxic). Not suitable for use in

In Examples 4 and 5, even when a tertiary amine compound having no dimethylamino group (EMBA, DCHMA) was used as an initiator, the tertiary amine compound had a disubstituted amino group NR(CH ₃ )- If the pKa of the disubstituted amino group is 8.0 or more, it indicates that gelation occurs within 120 minutes. However, the time required for gelation was longer than when a tertiary amine compound containing at least one dimethylamino group was used. Although DEMA (Comparative Example 3) falls under this case, it is not suitable for use in the present invention because its molecular weight is less than 100 and its volatility is high.

Comparative Example 1 shows that even if the tertiary amine compound contains a dimethylamino group, if the pKa of the dimethylamino group is lower than 8.0 (PMAN), the time required for gelation will exceed 120 minutes. It shows.
Furthermore, in Comparative Example 2, the disubstituted amino group of the tertiary amine compound does not correspond to NR(CH ₃ )- (the tertiary amine compound does not have a disubstituted amino group to which a methyl group is bonded). This shows that even if the pKa of the disubstituted amino group is 8.0 or higher (DEBA), the time required for gelation exceeds 120 minutes.

As is clear from the above, a resin containing a 2-methylene-1,3-dicarbonyl compound with a molecular weight of 180 to 10,000, which is difficult to proceed with the curing reaction due to the influence of steric hindrance, is used as a tertiary amine as an initiator. When curing with a compound, a suitable tertiary amine compound has a molecular weight of 100 to 1000 and has one or more disubstituted amino groups NR(CH ₃ )- to which at least one methyl group is attached, It is a tertiary amine compound having a pKa of 8.0 or more for at least one of its disubstituted amino groups.

10 Camera module 12 Lens 14 Voice coil motor 16 Lens unit 18 Support body 20 Cut filter 22 Image sensor 24 Printed wiring board 30, 32, 34 Adhesive

Claims (11)

A resin composition containing the following components (a) and (b).
(a) at least one 2-methylene-1,3-dicarbonyl compound, each of the following formula (I):

2-methylene-1,3-dicarbonyl compound having at least one structural unit represented by and having a molecular weight of 180 to 10,000 (b) Tertiary amine without at least one active hydrogen atom Compounds each having the following formula:

(In the formula, R ¹⁰¹ and R ¹⁰² each independently represent a monovalent hydrocarbon group (however, n-propyl group, isopropyl group, n-pentyl group, isopentyl group, n-heptyl group, isoheptyl group, n - excluding nonyl group, isononyl group, n-undecyl group, isoundecyl group and phenyl group))
A tertiary amine compound having a structure represented by the following, a molecular weight of 100 to 1000, and a pKa of 8.0 or more for the disubstituted amino group in the formula (excluding tetramethylguanidine) The composition according to claim 1, wherein the disubstituted amino group has a pKa of 9.0 or more. The composition according to claim 1 or 2 , wherein the tertiary amine compound is liquid at 80°C. The composition according to any one of claims 1 to 3 , wherein the tertiary amine compound is liquid at 25°C. The composition according to any one of claims 1 to 4 , wherein the amount of the tertiary amine compound is 0.01 to 30 mol% based on the 2-methylene-1,3-dicarbonyl compound. The composition according to any one of claims 1 to 5 , which is used for manufacturing electronic parts. An adhesive or a sealant comprising the resin composition according to any one of claims 1 to 6 . The adhesive or sealing material according to claim 7 , which is used for electronic components. A film or prepreg comprising the resin composition according to any one of claims 1 to 6 . The film or prepreg according to claim 9 , which is used for electronic parts. A semiconductor device comprising a cured product of the resin composition according to any one of claims 1 to 6 .